Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

The effect of Mo -> Nb substitution on the electronic structure of MoS2 nanotubes has been investigated using the density functional tight binding method (DFTB). It has been found that composite Mo1-xNbxS2 nanotubes (with Nb contents of 5, 10 and 25 at%) are more stable than the corresponding pure tubes, especially for larger tube diameters. The defect-formation energy indicates that the most stable dopant arrangement is a NbS2 stripe along the tube direction. However, entropy effects may favor a random arrangement of Nb dopant atoms at high temperatures in the tubes with a larger diameter. All of the studied Mo1-xNbxS2 nanotubes have metallic properties, independent of their chirality, diameters and ordering type of substitutional atoms.

Experimental and numerical studies of a gas-liquid two-phase flow were applied to a non-baffled laboratory-scale stirred tank reactor, mechanically agitated by a gas-inducing turbine. The dispersion of air as gas phase into isopropanol as liquid phase at room temperature under different stirrer speeds was investigated. The X-ray cone beam computed tomography (CBCT) measurements were taken at five different stirrer speeds starting from 1000 rpm at which the gas inducement occurs for the given operating conditions. The considerable difficulties in acquiring the phase distribution due to beam hardening and radiation scattering effects were overcame by developing a suitable measurement setup as well as by calibration and software correction methods to achieve high accuracy. The computational fluid dynamics analyses of the stirred tank reactor were performed in 3D with CFX 10.0 numerical software.

At the experimental heavy ion therapy facility (Gesellschaft für Schwerionenforschung Darmstadt, Germany) an in-beam PET scanner is operated for quality assurance monitoring simultaneously to the therapeutic irradiation. The fixed dual-head PET scanner, which is completely integrated into the treatment facility, registers the annihilation γ-rays following the decay of minor amounts of β+-radioactive nuclei produced via nuclear reactions between the ions of the therapeutic beam and the atomic nuclei of the irradiated tissue. From a comparison of the reconstructed activity distributions with those predicted from the treatment plan, deviations between the prescribed and the applied dose distributions can be detected. The quality assurance monitoring of the therapeutic irradiation could profit significantly of a very fast (ideally, real time) reconstruction algorithm and, therefore, an accurate knowledge of the system response function (system matrix) is required. These requirements lead to the development of a dedicated method of system matrix calculation which has to model the system response precisely and deliver system matrix values rapidly. By exploiting the system symmetries, in combination with an optimized interpolation and approximation strategies, the proposed method delivers the system response function in a continuous 3D image space with a high accuracy.

Slug flow as a multiphase flow regime can occur in the cold legs of pressurized water reactors, for instance after a small break Loss of Coolant Accident (SB-LOCA). Slug flow is potentially hazardous to the structure of the system due to the strong oscillating pressure levels formed behind the liquid slugs. It is usually characterized by an acceleration of the gaseous phase and by the transition of fast liquid slugs, which carry out a significant amount of liquid with high kinetic energy. For the experimental investigation of air/water flows, a horizontal channel with rectangular cross-section was build at Forschungszentrum Dresden-Rossendorf (FZD). Experimental data were used to check the feasibility to predict the slugging phenomenon with the existing multiphase flow models build in ANSYS CFX. Further it is of interest to prove the understanding of the general fluid dynamic mechanism leading to slug flow and to identify the critical parameters affecting the main slug flow parameters (like e.g. slug length, frequency and propagation velocity; pressure drop).

The OECD/NEA and AER coupled code benchmarks for light water reactors markedly contribute to the testing of best estimate coupled codes in reactivity transients. At the same time, these benchmarks and flow mixing studies indicate that further improvement of the mixing computation tools in the integrated codes is necessary.
Plant measured data from VVER-1000 coolant mixing experiments were used to test and validate CFD codes. The task is to compare the various calculations with measured data, using specified boundary conditions and core power distributions.
The experiments, which are provided for CFD validation, include single loop cooling down or heating-up by disturbing the heat transfer in the steam generator (SG) through the steam valves at low reactor power in the range of 5-14% and with all main coolant pumps (MCP) in operation. They were conducted during the plant commissioning phase at Kozloduy-6, Bulgaria and Kalinin-1, 2, Russia.
CFD calculations have been performed for the thermal hydraulic benchmark V1000CT-2 using ANSYS CFX. The numerical grid model was generated with the grid generator ICEM-CFD and contains 4.7 Mio. tetrahedral elements. The Best Practice Guidelines (BPG) in using CFD in Nuclear Reactor Safety Applications have been used. Different advanced turbulence models were used in the numerical simulation. The best agreement with the Kozloduy heating-up experiment at the core inlet shows the Detached Eddy Simulation (DES). Strong fluctuations occur in the downcomer of the RPV. The results show a clear sector formation of the affected loop at the downcomer, lower plenum and core inlet. The maximum local values of the relative temperature rise in the experiment amount 97.7% and in the calculation 97.3%. Uncertainties are still the estimation and interpolation of experimental values at the core outlet to the core inlet.

Nanocrystal memories are attractive candidate for the development of non volatile memory devices for deep submicron technologies. In a nanocrystal memory device, a 2D network of isolated nanocrystals is buried in the gate dielectric of a MOS and replaces the classical polysilicon layer used in floating gate (flash) memories. Recently, we have demonstrated a route to fabricate these devices at low cost by using ultra low energy ion implantation. Obviously, all the electrical characteristics of the device depend on the characteristics of the nanocrystal population (sizes and densities) but also on their exact location with respect to the gate and channel of the MOS transistor. It is the goal of this paper to report on the main materials science aspects of the fabrication of 2D arrays of Si nanocrystals in thin SiO2 layers and at tunable distances from their SiO2/interfaces.

In the present work FIB ion implantation of Co+ ions and subsequent anneaeling was applied to ion beam synthesis of CoSi2 nanowires with feature dimensions of about 20-50 nm in diameter and wire lengths of some µm. Using the CANION 31Mplus FIB column (Orsay Physics) a focusing of the Co++ ion beam down to a spot diameter of 30-50 nm was achieved. The ion energy was chosen to be 60 keV corresponding to a mean ion penetration depth of Rp = 33 nm. For the study of the conventional ion beam synthesis of CoSi2 nanowires (phase separation through precipitation and wire ripening during thermal treatment) and their decay into chains of nanoparticles due to nanowire instabilities the samples were implanted with high doses (1x1016-2x1017 cm-2) and at 420 °C sample temperature. Additionally, the scan direction of the FIB relative to the crystal directions was varied (normal FIB scan-direction was parallel to the [110]-direction on the Si surface). Small misalignment of the FIB trace relative to the [110] orientations leads to the decay of the CoSi2 nanowires into chains of more or less prolonged CoSi2 nanoparticles. Samples implanted at lower ion doses (1014-1016 cm-2) and at room temperature were used to investigate the influence of locally FIB induced irradiation defects on the CoSi2 nanowire growth. In this case, nanowires were again formed during thermal treatment by reacting of cobalt from a thin evaporated layer on the sample back side with defects induced by Co+ ion implantation with the FIB. The nanowires here are self-aligned along the in-plane [110] silicon crystal directions in (001)- and (111)-Si. In contrast to conventional ion beam synthesis of CoSi2 nanowires by high dose FIB implantation along a narrow trace defect-induced and self-aligned nanowire growth seems to be more stable.

Erläuterungen zum Kernbrennstoffkreislauf, zur Herstellung von Brennelementen sowie zur Funktionsweise von Reaktoren

After a long lasting period of uranium mining and production in Saxony and Thuringia, Eastern Germany, mines have fallen into disuse.
Soil, subsoil and waste waters of former mines and production sites contain still high concentrations of heavy metals and radionuclides, such as uranium. Besides chemical and physical factors influencing the mobility of uranium, also microbial metabolism plays a decisive role in enhancing or retarding migration effects. For instance bacteria are able to bind uranium on the cell surface, to accumulate uranium inside the cell, to reduce or oxidize uranium or to form insoluble uranium precipitates. Intensive studies on the uranium-microbe interaction allow on the one hand to obtain a more detailed understanding of the macroscopic behaviour of uranium in nature and on the other hand the development of new innovative bioremediation strategies for cleaning uranium contaminated water and soil. Starting from several examples of microbes interacting with uranium, the lecture will give an overview about bacterial detoxification strategies, the underlying molecular mechanisms and their application potential for bioremediation.

A pentathiophene-based swivel cruciform, which allows rotation between the cruciform arms, was synthesized. Homogeneous microcrystalline films were processed from solution, and field-effect transistors utilizing this dimer gave hole mobilities up to 0.012 cm2/V·s.

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Objective of this project was the study of interaction processes between humic substances, U(VI), Np(V) and kaolinite KGa-1b. It contributed to the attainment of a better process understanding, the improvement of the knowledge on the interaction of humic substances and metal ions and the enhancement of the thermodynamic database.
With a synthetic humic acid (HA), N-containing functional groups of HA were characterized by 15N-NMR spectroscopy. Based on these results, model studies of the influence of amino groups on the complexation behavior of HA were performed. Spectroscopic studies with amino acids show that the amino group do not contribute to the U(VI) complexation at pH 4.
The impact of kaolinite on the formation of HA and humic substance-kaolinite-sorbates was studied in model syntheses. The results exhibit that the presence of kaolinite during the syntheses mainly influences the yields on HA and their elemental compositions. Synthetic humic substance-kaolinite-sorbates were isolated.
Under exclusion of CO2, the U(VI) complexation by HA was investigated at pH 7 by means of the conventional time-resolved laser-induced fluorescence spectroscopy (TRLFS) and TRLFS with ultrafast pulses. Complexation parameters for the ternary complex UO2(OH)HA(I) were determined.
Studies of the Np(V) reduction in presence of HA with different functionalities under anaerobic conditions have shown that Np(V) is reduced to Np(IV) by HA. The redox capacity depends on the HA functionality. Applying a modified HA it was verified that phenolic/acidic OH groups play a dominating role in the Np(V) reduction.
The influence of HA on the U(VI) and Np(V) sorption onto kaolinite was investigated in batch experiments. In dependence on the experimental conditions, HA effects the sorption and consequently the mobility of U(VI) and Np(V). From studies of the U(VI) sorption onto synthetic humic substance-kaolinite-sorbates it was concluded that the structure and functionality of sorbed/associated humic substances considerably influence the sorption behavior of U(VI). The structure of U(VI)-kaolinite-surface complexes in presence of HA was studied by means of X-ray absorption spectroscopy and TRLFS and compared to those of U(VI)-kaolinite-complexes.
Investigations of the migration of HA and U(VI) in the laboratory system kaolinite-water were carried out in diffusion experiments. The migration of HA in compacted clay is governed by diffusion and influenced by its colloidal properties. Humic substances exert an immobilizing effect on the U(VI) transport in compacted kaolinite.

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This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60 K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between I and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.

A prototype system for radiobiological studies has been investigated. It is based on thermally stimulated exoelectron emission (TSEE) detectors and can be used for precise determination of the absorbed dose in a live cell monolayer of several µm thickness. In the present study, five types of BeO detectors, different in structure and method of production, were tested in combination with a Geiger-Müller counter. The dose response and dose range, reproducibility and long-time stability of response, as well as the applicability in a simulated cell culture environment have been studied. The dose response was found to be linear over two orders of magnitude and limited by the counter resolution. However, by a variation of detector sensitivity, the whole dose range of interest for radiobiological experiments can be covered. The irradiation in a simulated cell environment was successful only for one detector type. The system performance was found to be limited by the variation in the system response for time periods longer than several hours, therefore, it is suitable for absolute dose measurement with calibrated detectors if reproducible laboratory conditions are provided.

Two ceramics, zirconolite and a monazite-brabantite solid solution (MBss) were studied for the immobilization of minor actinides (Np, Am, Cm) produced by reprocessing spent fuel. Monoclinic zirconolite (CaZrTi2O7) is a fluorite derivative structure and is the primary actinide host phase in Synroc (a titanate composite). Monazite (LnPO(4), where Ln = La, Ce, Nd, Gd, etc.) is a monoclinic orthophosphate containing trivalent cations, and brabantite (Ca(0.5)An(0.5)PO(4)) is ail isostructural monazite compound containing tetravalent cations (An = Th and U). The nominal composition of the ceramics studied in this work is (Ca0.87Pu0.13)Zr(Al0.26Ti1.74)O-7 for zirconolite and (Ca0.09Pu0.09La0.73Th0.09)PO4 for the monazite-brabantite solid solution. These formulas correspond to 10 wt% PuO2 loading ill each material. XANES spectroscopy showed that the plutonium is tetravalent in zirconolite and trivalent in MBss. Thorium, another tetravalent cation, call be incorporated at 10 wt% ThO2 in MBss. Aluminum and calcium balance the excess cationic charge resulting from the incorporation of Pu(IV) in zirconolite and Th(IV) in brabantite, respectively. The relative density of the pellets exceeded 90% of theoretical density. The samples exhibited a homogeneous microstructure even if some minor phases. representing less than 2% of the surface area, were detected. The two ceramics are compared in terms of actinide loading, and preliminary results on their long-term behavior are discussed. (c) 2006 Elsevier B.V. All rights reserved.

High-level radioactive wastes produced by spent fuel reprocessing containing fission and activation products as well as actinides are incorporated in a borosilicate glass. To ensure optimum radionuclide containment, the resulting glass must be as homogeneous as possible. Microscopic heterogeneity can arise from various processes including the excess loading of an element above its solubility limit. The current actinide loading limit is 0.4 wt%. Work is in progress to assess the actinide solubility in these glasses, especially for plutonium. Initially the actinides were simulated by lanthanides and hafnium. The results show that trivalent elements (La, Gd) exhibit greater solubility than tetravalent elements (Pu, Hf). Cerium is an interesting element because its oxidation state varies from IV to III depending on the process conditions, such as the temperature and redox potential of the melt. In order to quantify the solubility increase, cerium-doped glass samples were melted under reducing conditions by adding a reducing agent. The solubility observed at 1473 K increased significantly from 0.95 to 13.00 wt%. Several reducing compounds have been tested. This paper deals with this study and the application to reduce Pu(IV) to Pu(III). The reduction state was characterized by X-ray absorption spectroscopy (XANES) for plutonium and by chemical analysis for cerium. The material homogeneity was verified by optical and scanning electron microscopy. Preliminary findings concerning the reduction of Pu-doped glasses fabricated in hot cells are also discussed. (c) 2006 Elsevier B.V. All rights reserved.

Applying a novel approach to the spectral analysis of Extended X-ray Absorption Fine Structure (EXAFS) we were able to derive an advanced 3-D structural model of the uranyl sorption complex on hydrated carbonate-free surfaces of aluminum(III) and iron(III) oxyhydroxide nanoclusters. The calculated molecular model fits the EXAFS data consistently up to a radial sphere of 4.5 Å around the uranium absorber. Being unaware of the physicochemical reasons for the specific complex topology characterized by a slightly tilted and distorted geometry, alternative ideas of EXAFS interpretation are discussed.

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The Rossendorf version of the CYCLONE 18/9 is equipped with a 2 m long external beam transport line (BTL) to have the possibility of producing non-standard PET radionuclides. For this purpose a solid target system was developed and mounted to the BTL. This system increases the flexibility of the CYCLONE 18/9 and enables the production of e.g. ⁸⁶Y and ⁵⁶Co for applications in radiochemistry, nuclear medicine and nuclear physics. The solid target system is introduced shortly and the parameters, data and results of the production of ⁸⁶Y and ⁵⁶Co are given.

In different scenarios of small break Loss of Coolant Accident (SB-LOCA), stratified two-phase flow regimes can occur in the main cooling lines of pressurized water reactors. Because these flow patterns cannot be predicted with the required accuracy and spatial resolution by the one-dimensional system codes, the stratified flows are increasingly modelled with computational fluid dynamics (CFD) codes. In CFD, closure models are required that must be validated, especially if they are to be applied to nuclear reactor safety. Because the structure of the interface is strongly connected with the momentum transfer between the phases, the water surface characteristics can be used for validation purposes. Experimental data suitable for CFD validation must satisfy special quality criteria, in particular the boundary conditions and the measurement resolution.

For the investigation of co-current two-phase flows at atmospheric pressure and room temperature, the Horizontal Air/Water Channel (HAWAC) was built at Forschungszentrum Dresden-Rossendorf. At the channel inlet, a special device was designed for a separate injection of water and air into the test-section. A blade separating the phases can be moved up and down to control the free inlet cross-section for each phase. This provides adjustable and well-defined inlet boundary conditions and therefore very good CFD validation possibilities.

The HAWAC facility is designed for the application of optical measurement techniques, which deliver the high resolution required for CDF validation. Therefore, the 8 m long acrylic glass test-section with rectangular cross-section provides good observation possibilities. High-speed video observation and particle image velocimetry (PIV) were applied during slug flow. The camera images show the generation of slug flow from the inlet of the test-section. An algorithm was developed to recognise the interface and the extraction of quantitative values, like water level and slug propagation velocity. The PIV measurements reveal the inner flow rotation inside a slug.

Parallel to the experiments, CFD calculations were carried out. The aim of the numerical simulations is to validate the prediction of slug flow with the existing multiphase flow models built in the commercial code ANSYS CFX. The Euler-Euler two-fluid model with the free surface option was applied to a grid of 600,000 control volumes. The turbulence was modelled separately for each phase using the k-ω based shear stress transport (SST) turbulence model. The results compare well in terms of slug formation, velocity, and breaking. The qualitative agreement between calculation and experiment is encouraging, while quantitative comparison show that further model improvement is needed.

To examine the influence of optical anisotropy on the near-field signal measured in a scattering-type scanning near-field optical microscope, we excite optically uniaxial LiNbO3 close to a phonon resonance at a wavelength of 13 µm in the infrared regime using a tunable free-electron laser. This allows us to excite a phonon polariton resonance in the coupled tip-sample system. We find that the resonance shows a clear dependence on the orientation of the optical axis of the birefringent crystal.

We present an approach for photoconductive THz generation providing a broad bandwidth and exceptionally high electric-field amplitude. A large-area interdigitated two-electrode structure on a GaAs substrate offers high electric fields at moderate bias voltages. In order to avoid destructive interference of the THz waves in the far field, every second electrode gap is masked by an additional metallization [1]. Thus all semiconductor regions exposed to incident radiation exhibit parallel electric fields and photocarriers excited by a mode locked Ti:Sapphire laser with MHz or GHz repetition rates are accelerated in the same direction. Areas with anti-parallel fields do not contribute to the THz radiation, thus the resulting constructive interference gives rise to an intense THz output. Using electro-optic sampling, we detect a THz field amplitude of 1.7 kV/cm, which is almost one order of magnitude higher as compared to previous photoconductive emitters excited with pulses from an unamplified oscillator. This field value corresponds to an average THz power of 145 µW and yields a NIR-to-THz power-conversion efficiency as high as 2 × 10-4. We have employed this emitter concept in a compact THz spectrometer based on asynchronous optical sampling (ASOPS) [2]. ASOPS allows us to scan the THz electric field over a nanosecond time delay at a kilohertz scan rate without using a mechanical delay stage. To this end, two mode-locked femtosecond lasers with approximately 1 GHz repetition rate are combined at a fixed, stabilized kHz difference frequency ∆f. One laser delivers the THz excitation pulse, the other provides the probe pulses for electro-optic detection. In this way, the relative time delay between the THz pulses and the probe pulses is linearly ramped, thus enabling high-speed scanning over a 1 ns time delay with the scan rate ∆f. At a scan rate of 9 kHz a time resolution of 230 fs is accomplished. High-resolution spectra from 50 GHz up to 3 THz are obtained and water absorption lines with a width of 11 GHz are observed. A dynamic range larger than 3 orders of magnitude is achieved in a few 10 seconds averaging time.
[1] A. Dreyhaupt, S. Winnerl, T. Dekorsy, M. Helm, Appl. Phys. Lett. 86, 121114 (2005).
[2] A. Bartels, A. Thoma, C. Janke, T. Dekorsy, A. Dreyhaupt, S. Winnerl, M. Helm, Opt. Express 14, 430-437 (2006).

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Nanowires (NWs) play an important role as basic components of electronic and photonic devices. Here, theoretical studies using atomistic computer simulations and experi¬mental results are presented on the CMOS-compatible fabrication of metal silicide and semiconductor NWs by focused ion beam (FIB) implantation and subsequent thermal annealing. The FIB implantation along a straight trace leads to a local and surface-near supersaturation in the substrate. Post-implantation annealing causes NW formation by self-organization. It is demonstrated that the evolution of the FIB implantation profile proceeds in three well-separated stages: (1) Phase separation by nucleation and growth, (2) NW formation by coalescence of nanoclusters, (3) NW surface smoothening. Likewise, components for functional devices involving several NWs, like T- or X-junctions, can be obtained by crossing different FIB traces. During long-term thermal annealing, NWs disintegrate into regular chains of nanoparticles (Rayleigh instability) that can be used as surface-plasmon-polariton waveguides. Crosses, corners or ends of NWs are subject to a preferential disintegration. Thus, structures suitable for single-electron-transistors and for multi-gate NW field effect transistors may be fabricated by crossing FIB traces.

Gibt es Möglichkeiten, die Bevölkerung vor den Folgen eines hypothetischen schweren Kernschmelzunfalls in einem Reaktor zu schützen? Welche Schutzvorkehrungen sind bisher vorgesehen? Neue Antworten auf diese Fragen werden in der Reaktorsicherheitsforschung erarbeitet. In diesem Vortrag werden die Ergebnisse einer Forschungsarbeit zur Rückhaltbarkeit von Kernschmelze im Reaktordruckbehälter eines großen Kernkraftwerks dargelegt.

The core model DYN3D which has been developed for three-dimensional analyses of steady states and transients in thermal reactors with quadratic or hexagonal fuel assemblies is based on nodal methods for the solution of the two group neutron diffusion equation. Loading cores with higher content of MOX fuel, the increase of the fuel cycle length, and the consideration of new reactor types are challenging for these standard methods. A nodal expansion method for solving the equations of the simplified P3 (SP3) approximation of the multigroup transport equation was developed to improve the accuracy of the DYN3D code. The method described in the paper is verified with pinwise calculations of a steady state of the OECD/NEA and U.S. NRC PWR MOX/UO2 Core Transient Benchmark. The used 16-group cross section library was generated for DORT calculations with homogenized pin cells. Two different approximations of the diffusion coefficient which occurs in the within-group form of the SP3 equations are investigated. Using the transport cross section for the calculation of the diffusion coefficient gives much better results than those obtained with the removal cross section. The improvement of the results in comparison to a pinwise diffusion calculation is shown. The results are compared with the DORT and the heterogeneous reference solution of the code DeCART. Concerning the SP3 calculation using the diffusion coefficient based on the transport cross section (DYN3D-SP3-TR) the deviations of the eigenvalue keff and the assembly powers from the transport solutions of DORT and DeCART are in the same order as those between the two transport solutions themselves. The improvement of the DYN3D-SP3-TR results in comparison to the diffusion calculation is presented. As the DYN3D-SP3-TR and DORT calculations are performed with homogenized pin cells, the pin powers of the two calculations are closer to each other than to the pin powers of the DeCART solution. To estimate the contribution of higher flux moments, the ratio of the second flux moment to the zeroth flux moment is investigated along a horizontal row of pins. It is shown that it is low in the fuel assemblies with small peaks at the water channels. Considering the baffle and the water reflector regions higher values are obtained in the fast neutron groups.

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Background: Impaired glucose tolerance (IGT) is associated with an increased risk of atherosclerosis that may be due in part to dyslipidemia. The purpose of this study was to assess the regulatory role of lipid transfer proteins in the development of this dyslipidemia. Methods: Activities of cholesterol ester transfer protein (CETP) and phospholipid transfer protein (PLTP), as well as lipid and protein components of the major lipoprotein fractions, were evaluated in probands with IGT and were compared with those in subjects with normal glucose tolerance. The effect of a fat-rich meal on these variables was also investigated. Results: IGT probands had a higher triglyceride content in subfractions of low- (LDL) and high-density lipoprotein (HDL). IGT patients had higher fasting CETP activity. The latter was positively correlated with HDL2 triglycerides and negatively with HDL3 total cholesterol. PLTP activity and mass were not higher in IGT patients. However, PLTP activity correlated with components of VLDL and LDL and was influenced by the type of obesity. Neither CETP and PLTP activities nor PLTP mass were altered by a fat-rich meal. PLTP and CETP activities correlated in both fasting and postprandial conditions. Conclusions: Increased fasting CETP activity may contribute to increased risk of atherosclerosis in subjects with IGT.

Nickel plays a key role in the degradation mechanism of neutron-irradiated reactor pressure vessel steels. Binary Fe-Ni alloys are basic for understanding and modeling of the behaviour of more complex steels. The nature of irradiation-induced features in Fe-3wt%Ni was investigated by means of small-angle neutron scattering and Vickers hardness measurements and compared with results for commercially pure Fe. We have observed a vacancy-Ni ratio of 0.4 to 0.5 in the average scatterer. This finding is consistent with the hardness increase observed.

In this cycle study the Pu production in the German reactor park will be analyzed and compared to different limiting scenarios. The effects on the Pu production due to a postulated lifetime extension of roughly 10 years are discussed.

Durch Laborexperimente und durch den Vergleich mit der geochemischen Erfahrung wird die Rolle von U(IV)- und U(VI)-haltigen Kolloiden für radioaktive Endlager und für stillgelegte Uranbergwerke analysiert. Gezeigt wird, dass in der natürlichen Umwelt sowohl transportunterstützende Einflüsse von Kolloiden auf „immobile“ radiotoxische Kontaminanten wie Uran(IV) als auch transporthemmende Einflüsse auf „mobile“ radiotoxische Kontaminanten wie Uran(VI) möglich sind. Bei Performance-Asssessment-Berechnungen für radioaktive Endlager stehen die transportfördernden Einflüsse der Kolloide im Vordergrund, transporthemmende werden meist vernachlässigt. Für Bergwerke dagegen sind, neben transportfördernden auch transporthemmende Kolloideinflüsse (Natural Attenuation) von großem Interesse, denn sie können in Remediationsstrategien ausgenutzt werden.

MoS2 nanoplatelets have catalytically active sites along their edegs that are promising for desulfurizing fuels

Ti6Al4V specimens have been irradiated at different temperatures with 200 keV He ions. Microhardness and elastic modulus of the unirradiated and irradiated specimens were measured by means of the nano-indentation technique and analyzed using the Oliver-Pharr method. The indentation depth of all samples is 700 nm, which is comparable in magnitude to the ion range. The subsurface structure of the Ti6Al4V specimens was investigated by the X-ray diffraction technique. The measurements indicate that the microhardness increased with the irradiation temperature from room temperature to 600 degrees C while the elastic modulus almost monotonically decreased. The Irradiation at 700 degrees C, however, caused softening and slight increase of the elastic modulus within the surface layer of the specimens. The hardening and reduction of the elastic modulus of the Ti6Al4V alloy under irradiation conditions used in this study is tentatively explained by a model based on the presence of point defects and dispersed obstacles of P-precipitates. The softening and slight increase of elastic modulus of helium-irradiated Ti6Al4V at 700 degrees C might be related to the coarsening of beta-precipitates and formation of the hybrid gamma-TiH phase in alpha-phase.

The development of spatial dynamics code for Molten Salt Reactors (MSR) is reported in this paper. The graphite-moderated channel type MSR - one of the 'Generation IV' concepts - was selected for the numerical simulation. It has several peculiarities (e.g. the drift of delayed neutrons precursors), which disable the use of standard dynamics codes. Therefore, the own DYN3D-MSR code was developed. It is based on the light water reactor code DYN3D and it allows transients simulation by 3D neutronics and parallel channel thermal-hydraulics. The neutronics and thermal-hydraulics were modified for the MSR peculiarities, where the experience from DYN1D-MSR development was exploited. The code was validated on experimental results from the MSRE experiment done in Oak Ridge National Laboratory and by the comparison with other codes especially with the 1D version. However, by the 3D code transients can be simulated, where space-dependant efforts are relevant, like local blockage of fuel channels or local temperature perturbations.

This work focuses on the role of the native oxide layer (SiO2) on the nickel (Ni)-assisted crystallization of amorphous silicon (a-Si). In some samples, the native oxide was removed using a HF-diluted solution before Ni layers with 0.5 nm be deposited on a-Si. The results show that the presence of a thin SiO2 layer of about 3 nm between the a-Si and the Ni delays the crystallization process. Ellipsometry data show that, after annealing for 5 h at 500 °C, the HF-cleaned sample presents a crystalline fraction of 88%, while the one with the native oxide has only 35%. This difference disappears after 20 h where both samples present similar crystalline fraction. These facts are also reflected on the film's electrical properties, where the activation energy for samples annealed for 5 h rises from 0.42 eV to 0.55 eV, when the oxide layer is removed. After 20 h and 30 h, the activation energy is around 0.55 eV for both kinds of samples, meaning that films with similar electrical properties are now obtained. However, the XRD data suggest the presence of some structural differences attributed to slight differences on the crystallization process.

Conductivity wire-mesh sensors have been successfully employed in the investigation of two-phase flows in the past. Since the measuring principle requires at least one continuous conductive phase, wire-mesh sensors have almost exclusively been used for the investigation of air-water or steam-water systems. Nevertheless, non-conducting fluids such as oil or organic liquids often occur in industrial applications, for instance, in chemical and petrochemical industry. The experimental investigation of multiphase flows involving non-conducting fluids is therefore of large interest. For this reason we developed a novel wire-mesh sensor based on measurements of the electrical permittivity (capacitance) which is suitable for the investigation of non-conducting fluids. The prototype sensor consists of two layers of 16 steel wires each. The system can at the moment produce cross-sectional phase distribution images with 625 frames per second. Sensor and associate electronic were evaluated showing good accuracy and reproducibility in the permittivity measurement. Initial results of an air-oil bubbly flow as well as a slug flow measurement are presented.

A flash lamp has been used to uniformly anneal large wafers with diameters approaching 100 mm. The equipment applies a pulse, with duration of 3-20 ms, resulting in large transient thermal gradients in the wafer. In this paper, we present separate models of the thermal reaction of this process and its effect upon the mechanical behavior, in order to predict stresses and shape changes, and to capture practical phenomenon. We further use the model to follow changes in the expected response consequent on altering process conditions, such as preheating and pulse duration, as well as exploring important issues associated with scaling to large wafer sizes. This work presents an initial description of the thermomechanical response of wafers to flash lamp annealing in the millisecond time regime and is therefore fundamental to the use of this technique in the fabrication of semiconductor devices.

We report the results of recent research that we have undertaken to increase our understanding of key actinide and fission product speciation in a range of ionic melts. These results will be used to develop novel electrochemical methods of separation of uranium and plutonium from irradiated nuclear fuel. Our studies in high temperature alkali metal melts (including LiCl and the eutectics LiCl-KCl and CsCI-NaCl) have focussed on in-situ speciation of U, Tc and Ru using both Electronic Absorption Spectroscopy (EAS) and X-ray Absorption Spectroscopy (XAS). The XAS studies have included Extended X-Ray Absorption Fine Structure (EXAFS) and X-Ray Absorption Near Edge Structure (XANES) measurements. We report what could be unusual uranium speciation in high temperature melts and evaluate the likelihood of Ru or Tc volatilisation during plant operation. Our studies in lower temperature melts, commonly known as ionic liquids, have focussed on salts containing tertiary alkyl group 15 cations and the bis(trifluoromethylsulphonyl)imide anion, melts which we know to have exceptionally wide electrochemical windows. We report Ln, Th, U and Np speciation (XAS, EAS and vibrational spectroscopy) and electrochemistry in these melts.

For the measurement of fluid distributions inside a hydrodynamic coupling we have developed a high-speed surface sensor based on the measurement of the electrical conductivity. Two sensors are placed on the pressure-side and the suction-side walls of a blade channel inside the coupling. The sensors are composed by approximately 1000 interdigitated sensing structures. The system is supplied by a battery and has a wireless link to communicate with a PC. Sensor and electronics have been so designed that the whole system can rotate together with the coupling pump wheel. The electronics measures the conductivity of the liquid of each sensing structure in a multiplexed manner which effectively gives images of the instantaneous liquid distribution over the sensor surface. Frame frequencies of up to 10,000 images per second can be reached. We have applied the surface sensor to measure the fluid distribution in a test coupling for different slip conditions. Initial results are presented and discussed.

The Munich Accelerator for Fission Fragments is planned to be installed at the FRM II in Garching. It will operate a uranium-carbide-loaded graphite matrix as a target for neutron-induced fission. The radioactive reaction fragments leave the ion source as both, atoms and ions. For radiation safety it is imperative to have a basic understanding of the fragment distribution within the beam line.

Atoms leaving the graphite matrix will spread like a gas and stick to surfaces depending on their species. A probabilistic Monte-Carlo approach is used to predict the surface coating of internal surfaces of the beam line for all fission nuclides. To decrease calculation time, the problem is reduced to two dimensions with the surface areas being a measure for the probability, that they are hit by a particle. The program is completely time dependent to implement radioactive decay.

Ions leaving the fission ion source are transported by electrostatic means towards the mass pre-separator, a low-resolution dipole magnet with a complex slit system in the focal plane. All unwanted ions are stopped at the slits, resulting in a high level of radioactive contamination. While it is advantageous for shielding purposes to have the majority of the contamination in one point, precautions must be taken to ensure that it stays that way. Material corrosion caused by sputtering will release previously implanted radionuclides. To reduce this effect, different methods are under investigation, one of which is changing the slit geometry. The considered designs will be described and experimental results will be shown.

A detailed account on the distribution of radioactive nuclei in the vacuum system of the planned Munich Accelerator for Fission Fragments (MAFF) located at the FRM-II research reactor is presented. Tools used for the simulation of spacial and temporal distribution of radionuclides are explained. The latter allows for a detailed activity budget as well as estimates for the mass-separated ion yields at MAFF. Additionally, a concept to reduce the activity release from the MAFF slit system due to surface sputtering is presented. It is shown, that the use of low-density carbon foam, as a surface coating, reduces sputtering by orders of magnitude.

A focused ion beam (FIB) has been applied to the fabrication of polymer microtubes via the rolling-up technique from poly(4-vinyl pyridine)/polystyrene bilayer films deposited on the top of a sacrificial aluminum layer covering a silicon wafer. The bending forces in the film arise due to different swelling of the bilayer components in acidic water and lead to rolling of the film. The dimensions and position of the rolled-up tubes can be controlled by FIB milling (sputtering) of geometrically well-adjusted openings in the polymer films. This technique can be applied to the structuring of scrolled films formed from different materials without the use of lithographically patterned photoresists. The geometrical patterning of the tube interior can also be done by FIB irradiation.

For industrial, environmental and public health purposes, actinide chemistry has been the subject of considerable efforts since the 50’s. Aqueous redox chemistry, ionic selective recognition, uptake by specific biomolecules or compartments of the geosphere are some of the major fields of investigation. The physical-chemical properties of the actinide elements strongly depend on the 5f/6d electronic configuration. Some of them (U, Np, Pu and Am) can form AnO2n+ (n= 1, 2) oxocations, so-called actinyls, with two strong An-O covalent bonds. In any case, the cation polyhedron is characterized by large, flexible coordination spheres with various stable and metastable metal oxidation states. Protactinium, as the first actinide with 5f-electrons involved in bonding, occupies a key position in the actinide series. At formal oxidation state V (its most stable oxidation state in solution as well as in the solid state) Pa(V) corresponds to the formal 5f0 electronic configuration. U(VI) also corresponds to the formal oxidation state 5f0 and is most often encountered as the stable oxocationic form UO22+. The first stable form of U, Np or Pu at formal oxidation state (V) under atmospheric conditions is NpO2+ with formal 5f2 electronic configuration. U(V) is highly unstable under atmospheric conditions and Pu(V) dismutates into Pu(IV) and Pu(VI). On the other hand, the existence of the PaO2+ form in solution and in solid state is highly improbable and has never been reported. In solution, XAFS at the actinide LIII edge is an ideal structural probe of the cation coordination sphere. Furthermore, coupling the XAFS data with molecular dynamics calculations leads to a better description of the cation-solvent interactions. In addition, disorder can explicitly be taken into account using time spaced snapshots of the molecule. This is particularly important when large polyhedra are composed of ligands of similar types as water molecules. This presentation addresses the structural characterization of actinide cations at oxidation states (V) and (VI) as one walks across the periodic table from Z = 91 (protactinium) to Z = 94 (plutonium). For the fist time to our knowledge, the occurrence of the oxocation form of Pa(V) in H2SO4 solution has been inferred from EXAFS and XANES data at the Pa LIII edge. A structural comparison between Pa, U, Np and Pu oxocations in aqueous solution at formal oxidation states (V) and (VI) is carried out. These results are corroborated by quantum chemical and molecular dynamics calculations.

The coordination behaviour of the uranyl ion UO22+ has regained interest due to the problem of nuclear waste management and environmental issues. At the end of the nuclear fuel cycle, reprocessing of the spent nuclear fuel mainly occurs by means of liquid-liquid extraction. During the PUREX process, the spent fuel is dissolved in a nitric acid solution. Uranium is extracted from the aqueous nitric acid fuel solution with an organic phase containing tri-n-butylphosphate (TBP; extracting agent). However, little is known about the structure of the chemical species involved in the liquid-liquid extraction process. The first coordination sphere of the uranyl ion UO22+ in UO2(NO3)2(TBP)2 was studied using UV-Vis absorption spectroscopy, EXAFS spectroscopy and 31P-NMR. The characteristic vibrational fine structure in the UV-Vis absorption spectrum points at a high symmetrical complex. The uranium polyhedron is composed of two axial oxygens located at 1.77 ± 0.01 Å, four nitrate (bidentate) oxygens at 2.52 ± 0.01 Å and two phosphate oxygens (TBP) located at 2.38 ± 0.01 Å.

The first coordination sphere of the uranyl cation in room temperature ionic liquids "IL's" results from the competition between its initially bound counterions, the IL anions, and other anions (e.g. present as impurities, or added to the solution). We present a joined spectroscopic (UV-visible and EXAFS) – simulation study of the coordination of uranyl initially introduced either as its UO2X2 salts (X- = nitrate NO3-, triflate Tf-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium – based ILs (A- = PF6-, Tf2N-, BF4-), as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. For instance, in the BumimTf2N liquid, UO2(SO4) is insoluble, the UO2(NO3)2 salt dissolves without dissociation, while the UO2(Tf)2 and UO2(ClO4)2 salts are soluble, likely in their complexed and dissociated form, respectively.

U(IV) hexachloro complexes were studied in hydrophobic room temperature ionic liquids [BuMeIm][Tf2N] and [MeBu3N][Tf2N] to determine their structure, speciation and redox properties (BuMeIm+ and MeBu3N+ are 1-butyl-3-methyl-imidazolium and tri-n-butylmethylammonium respectively, and Tf2N- is bis(trifluoromethyl-sulfonyl)imide).
As the Tf2N- anion is known to be a weak ligand exhibiting oxygen coordination as 1-O or 2-O,O to actinides or lanthanides, the U(IV) chloro complex could be under the general chemical form UClx(Tf2N)y(4-x-y).
The diffuse UV-vis solid state reflectance of both U(IV) complexes agree closely with the absorption spectra obtained in ionic liquids. It is well known that U(IV) hexachloro complex has a centrosymmetric octahedral arrangement in the solid state as well as in acetonitrile solution. It can be concluded that octahedral anion UCl62- is the predominant form of U(IV) in Tf2N- based ionic liquids. EXAFS measurements were also performed to investigate the coordination sphere of U(IV) chloro complex in [BuMeIm][Tf2N]. The results confirmed that the octahedral complex UCl62- is the predominant chemical form of U(IV) in Tf2N- based hydrophobic ionic liquids and a competing reaction with Tf2N- can be excluded. The U-Cl distance measured in [BuMeIm][Tf2N] is 2.632(2) Å and is slightly longer than that in solid state. Probably, it can be related to some stronger H-bonding of UCl62- with BuMeIm+ cation in ionic liquid than that of solid.

The elemental redistribution and Ge loss in low-energy Ge⁺ implanted SiO₂ films during wet-chemical cleaning and annealing procedures are investigated. Two effects of major importance for Ge nanocrystal formation have been found. Moisture components (H₂O vapor, H⁺, OH^-) penetrate into the damaged oxide during storage, wet chemical cleaning or annealing procedures and lead to a hydrogen and oxygen enrichment in the near-surface oxide. Furthermore, atomic collisions during Ge implantation result in an oxygen excess (with respect to SiO₂ stoichiometry) underneath the Ge profile. The local net ratio of Ge and excess oxygen determines, whether the implanted Ge is incorporated into the SiO₂ network as spatially fixed GeO₂, oxidizes to mobile GeO or remains as elemental Ge forming nanocrystals. Apart from very shallow profiles, where a drastic Ge loss is observed simply by cleaning in chemical solutions containing H₂O₂, the main Ge loss occurs during annealing. The highly mobile GeO is identified to be responsible for both, Ge redistribution or even loss, if diffusing GeO meets the SiO₂ surface and emanates into the annealing ambient. Annealing in Ar/H₂ mixtures at < 900°C reduces the Ge loss due to the reduction of Ge oxides. The enhanced Ge mobility (as GeO) is described as an oxygen vacancy assisted mechanism which also explains the influence of the Si/SiO₂ interface on the Ge diffusivity. Finally, the consequences of Ge redistribution and loss for Ge nanocrystal memory device fabrication are discussed.

The six-fold ring clustering in sp2-dominated pure carbon (C), nitrogenated carbon (CNx) and nickel alloyed carbon (C:Ni) thin films is investigated by Raman spectroscopy as a function of substrate temperature. Films have been grown by direct and dual ion beam sputtering, ion beam assisted evaporation and magnetron sputtering, resulting in amorphous, graphite-like, fullerene-like, paracyanogenlike, and in the case of C:Ni films – nanocomposite - structures.
Raman spectra in the wave-number region of 900–2000 cm−1 exhibit usually two main peaks positioned at ~1360 and ~1560–1590 cm−1 which are denoted conventionally by D and G, respectively, the G peak corresponding to in-plane bond stretching vibrations (it can be present in aromatic clusters as well as in chain structures) and the D peak corresponding to breathing vibrations of aromatic rings (it can be present only in ring structures). The total intensity of these peaks is proportional to the amount of the sp2 phase, while their relative ratio provides the information on the six-fold ring cluster size.
The results show that each type of atomic arrangement results in a characteristic set of the Raman spectra parameters, which describe the degree of aromatic clustering, bond length and angle distortion and order in sixfold structures1.
In the case of pure C films, the atomic structure evolves with substrate temperature from a disordered network to nanocrystalline planar graphitic configurations, with a progressive promotion in size and ordering of sixfold ring clusters1.
Nitrogen incorporation favors the promotion of sixfold rings in highly disordered networks produced at low temperatures, but precludes the formation of extended graphite-like clusters at elevated substrate temperatures (>400°C). In the latter case, N introduces a high degree of disorder in sixfold ring clusters and enhances the formation of a fullerene-like microstructure1.
The presence of Ni slightly favours the six-fold ring clustering at low temperatures (<300°C), while Raman spectra at higher temperatures have similar features for both C and C:Ni films. For deposition temperatures lower than 300°C, the the absolute intensity of the D-G band decreases by more than one order of magnitude despite the similar total amount of deposited material and one additional Raman line at around 1100 cm-1 appear indicating the presence of new carbon structures in the film. This correlates with the Ni segregation into nickel carbide or nickel nanoparticles occurring at T~300°C, thus segregated Ni and C phases may undergo separate ordering paths at higher temperatures. In contrast, a mixed C-Ni phase is formed at lower temperatures and the precipitation C sp2 phase is hindered.
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References:
1. G. Abrasonis, R. Gago, M. Vinnichenko, U. Kreissig, A. Kolitsch, and W. Möller, Phys. Rev. B 73, 125427 (2006).

N diffusion in austenitic stainless steel (ASS) under low energy Ar ion bombardment is investigated. ASS samples were ion beam nitrided at 400°C with the N ion energy of 1 keV and flux of 3.11015 s-1 cm-2. The nitriding time was adjusted to obtain a thickness of the nitrided layer of ~1m. The samples were subsequently annealed at 400°C under simultaneous 700 eV Ar+ bombardment with different fluxes (1.3-3.8×1015 s-1 cm-2). N depth profiles were obtained using nuclear reaction analysis, and the phase structure was measured using X-ray diffraction (XRD). XRD reveals the modified layer to be composed of only γN phase in both as-nitrided and Ar+ irradiated samples, with no evidence of nitride formation. It is observed that Ar+ bombardment increases the N mobility in the depths far beyond the ion penetration depth, resulting in an increased broadening of the N depth profile as a function of Ar+ flux. This effect cannot be explained by any established mechanism of radiation enhanced diffusion. Another set of samples was annealed at 400°C under low flux (4×1011 s-1 cm-2) 700 eV Ar ion bombardment of variable charge state (from 1+ to 8+). These charge states correspond to the potential energies of 16-578 eV. The latter is dissipated by electronic excitations in metals. It was found that low flux Ar ion bombardment enhances the N mobility; however, the ion potential energy does not play any role on deep N diffusion. The latter indicates that N diffusion enhancement over large distances (~1 m) is due to nuclear collisional processes during ion stopping in the matter. Tentatively, the observed phenomenon is discussed in terms of collisionally induced quasi-particles which propagate large distances from the layers directly affected by ion bombardment enhancing interstitial N diffusion.

The functional S-layer protein gene slfB of the uranium mining waste pile isolate Bacillus sphaericus JG-A12 was cloned as a PCR-product into the expression vector pET Lic/Ek 30 and heterologous expressed in E.
coli Bl21(DE3). The addition of His-tags to the N- and C-termini enabled the purification of the recombinant protein by Ni chelating chromatography. The Ni-binding capacity of the His-tagged recombinant S-layer protein was compared with that of the wild-type S-layer. The ICP-MS analyses demonstrate a significantly enhanced Ni-binding capability of the recombinant protein. In addition, the self-assembling properties of the purified modified S-layer proteins were studied by light microscopy and SEM. Whereas the wild-type S-layer proteins re-assembled into regular cylindric structures, the His-tagged S-layer proteins reassembled into regular sheets that formed globular agglomerating structures. The nanoporous structure of the protein meshwork together with its enhanced Ni-binding capacity makes the recombinant S-layer attractive as a novel self-assembling biological template for the fabrication of metal nanoclusters and construction of nanomaterials that are of technical interest.

In this work, we studied the oxide scales of AISI 304 and AISI 316 stainless steels formed under hightemperature aqueous conditions using X-ray photoelectron spectroscopy (XPS) together with sputter depth profiling. Two samples of SS 304 and 316 were prepared by exposing them to water at 300 °C containing 100 ppm boric acid and 7 ppm lithium hydroxide in an autoclave. In the case of sputtering with 3 keV argon ions, the elemental distribution as a function of the sputtering time was obtained. The formation of two oxide layers was observed – one mainly iron-based on top, and a second at a greater depth, consisting mainly of chromium-iron oxides. The depth scale of the profiles was calibrated by measuring the oxygen profile using Rutherford backscattering spectroscopy (RBS). On the basis of the distribution of the three oxidised alloying constituents (Fe, Cr, Ni) with respect to depth and elemental state, a relative increase of Fe2+ at the surface was found, while the chromium was depleted at the surface and Cr3+ tended to increase at the oxide/substrate interface. In order to estimate possible ion-beam-induced effects due to the ion sputtering, the profiles were compared to the computer-simulated ones obtained by a dynamic TRIM computer code. The simulations included only collisional effects during the sputtering process.

The improbable scenario of a severe accident with core meltdown and formation of a melt pool in the lower plenum of a Light Water Reactor (LWR) Pressure Vessel (RPV) can result in the failure of the RPV and the discharging of the melt to the con-tainment. One accident management strategy could be to stabilize the in-vessel de-bris or melt pool configuration in the RPV as one major barrier against uncontrolled release of heat and radionuclides into the containment of the plant.
Based on the successful simulation and analysis work of the FOREVER-experiments the models have been developed further to simulate the prototypical scenario of an In-Vessel-Retention in large PWRs. Based on recently observed results of the METCOR-Experiments it is known that the vessel wall ablation in case of melt-wall-contact can take place well below the steel melting point of T = 1493 °C. The FE-model developed at FZD is now improved to consider the time dependent thermo chemical wall ablation process.

This paper describes model experiments with low melting point liquid metals as an important tool to investigate the flow structure and related transport processes in melt flows being relevant for metallurgical applications. Three examples have been selected to demonstrate the benefit of such experiments, namely the electromagnetic stirring of a metallic melt in a pool, the directional solidification of Al-Si alloys under the influence of an electromagnetically driven flow and the behaviour of a liquid metal bubble plume if a vertically traveling field is applied. Results of flow measurements will be presented and the relevance for metallurgical processes will be discussed.

Understanding the migration behavior of actinides is important for the reliable long-term risk assessment of potential nuclear waste repositories. Humic acids (HA) comprise an important part of natural organic materials. HA are soluble in the pH range of natural waters and have the ability for complex and colloid formation. Due to these properties HA can affect the speciation of actinide ions, and therefore, their migration in the environment. In the present study we investigated the influence of HA on the U(VI) sorption onto kaolinite.
We used time-resolved laser-induced fluorescence spectroscopy (TRLFS) in order to characterize the species of U(VI) adsorbed onto kaolinite in the absence and presence of HA. Two adsorbed U(VI) surface species on kaolinite were identified in the pH range of pH 5.0 to pH 8.5. Obtained results help to improve the understanding of the geochemical interactions of hexavalent actinides in environment.

We explore the influence of geometrical variations on the structure and the time-dependence of the magnetic field that is induced by kinematic alpha² dynamos in a finite cylinder. The dynamo action is due to an anisotropic alpha tensor which can be derived from an underlying columnar flow. The investigated geometry variations concern, in particular, the aspect ratio of height to radius of the cylinder, and the thickness of the annular space to which the columnar flow is restricted. Motivated by the quest for laboratory dynamos which exhibit Earth-like features, we start with modifications of the Karlsruhe dynamo experiment. Its dynamo action is reasonably described by an alpha² mechanism with anisotropic alpha tensor. We find a critical aspect ratio below which the dominant magnetic field changes from an equatorial dipole to an axial dipole. Similar results are found for alpha² dynamos working in an annular space when a radial dependence of alpha is assumed. Finally, we study the effect of varying aspect ratios of dynamos with an alpha tensor depending both on r and z. In this case only dominant equatorial fields are found and most of the solutions are oscillatory, contrary to all previous cases where the resulting
fields are steady.

Defect engineering for SiO2 precipitation was investigated during ion beam synthesis in the first stage of SIMOX fabrication. Vacancy-type defects were created in Si: (i) a buried nanocavity layer was pre-fabricated by He implantation and subsequent annealing, and (ii) excess vacancies were generated during oxide synthesis by an additional simultaneous high-energy Si irradiation.
A narrow nanocavity layer was found to be an excellent nucleation site that favors effectively the SiO2 formation. Such a cavity layer must be adjusted to the excess vacancy profile of the O implant. The excess vacancy generation by simultaneous dual implantation minimizes the defect production in Si. However, it is inappropriate to form a narrow oxide layer due to the too broad distribution of excess vacancies.

For the analysis of air-water bubbly flows in vertical pipes a method is presented which determines the radial profiles of velocity and angular displacement of the gaseous phase. Measurements rely on two so-called wire-mesh sensors, put into the flow behind each other and capturing the electrical conductivity distribution in the pipe cross-section at two different axial positions. The time-resolved signal is directly translated into transient two-dimensional distributions of the gaseous phase at both sensor positions. Sensor data analysis is based on two-dimensional cross-correlation within concentric cylindrical planes. The axial and angular displacement of the gaseous phase manifest themselves as the maximum position of the cross-correlation function.

Ultra-thin metal films are widely utilised for surface-enhanced Raman scattering and surface adsorption spectroscopy. We present in situ spectroscopic ellipsometry investigations of the growth of ultra-thin silver films, from island growth through percolation and continuous film growth. Silver films are deposited using a pulsed filtered cathodic vacuum arc, which provides precise control and reproducibility of the film growth conditions. Plasmon polariton resonances are determined for the growing islands below the percolation threshold. As the surface coverage increases a second oscillator, attributed to bulk plasma resonances, is required to accurately model the ellipsometric data. Postdeposition optical and electronic changes are observed for island films and the origins of these changes are investigated using the ellipsometric data

Although, most of the work reported on two-phase flows are limited to small pipe diameters, two-phase flow in large risers are increasingly being encountered in the petroleum and nuclear industries. In the present work, a wire mesh sensor was employed to obtain void fraction and bubble size distribution data and visualizations of steam/water flow in a large vertical pipe (194mm in diameter) at 46bar. For comparison purposes, measurements were made at similar phase velocities and physical properties to the data of Omebere-Iyari et al. (2006), which is for the flow of a nitrogen/naphtha mixture in a similar-sized riser. There exist significant differences between both sets of data. Churn-turbulent flow is observed in the present work instead of slug flow which differs from the intermittent and semi-annular flow patterns reported by Omebere-Iyari et al. (2006). The mean void fraction of the nitrogen/naphtha data is higher that of the present steam/water data. On examination of radial void fraction profiles, core peak distributions are observed for the present work in contrast to the wall peak profiles predicted for the data of Omebere-Iyari et al. (2006) using a power law relationship.

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X- ) nitrate NO3 -, triflate TfO-, perchlorate ClO4 -) or as UO2 (SO4) in a series of imidazolium-based ILs (C4mimA, A- ) PF6 -, Tf2 N-, BF4 - and C4mim ) 1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and Xanions.
Furthermore, the comparison of UO2Cl4 2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4
Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion’s degradation, showing that UO2F4 2- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmCl p 2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

General understanding needs to be deepened of intramolecular interactions engaged in molecular actinide species, i.e. physical chemical mechanisms that drive the affinity of chelating ligands for actinide cations still needs to be deepened. In this field, X-ray absorption spectroscopy has been extensively used as a structural and electronic metal cation probe. Combination with more traditional spectroscopic techniques such as spectrophotometry is an ideal tool for the understanding of the chelation mechanism. Metallobiomolecules are considered elaborate inorganic complexes with well-designed metal active sites. Although the various interaction processes between essential cations important to biology and proteins are widely studied, focus on the actinides is more seldom. Actinide impact on biological cycles has been motivated by risk assessments related to the wide use of nuclear fuel sources and industrial or military applications. In particular, the interaction between these cations with the biological active complexation sites are only partially understood.

A spectro-electrochemical cell was developed in order to study the speciation of radio-elements in thermodynamic unstable redox states using in situ XAS spectroscopy. This cell was used for the speciation of Re and Tc complexes in chloride media. Experiments on Re were carried out with the aim to validate the functionality of the experimental set-up. During electro-reduction of Re(VII) in HCl media, EXAFS and XANES studies were performed in order to reveal the formation of chloro-oxygenated compounds of Re(IV). The speciation of technetium in aqueous solutions of deep geological deposits for radioactive waste is important to predict its mobility under reducing conditions. XANES spectra showed that electro-reduction of Tc(VII) in chloride media leads to a position of K-edge absorption which agrees with a Tc(IV)/Tc(III) mixture.

Wie kann die Bevölkerung vor den Folgen eines hypothetischen schweren Kernschmelzunfalls in einem Reaktor geschützt werden? Welche Schutzvorkehrungen sind vorgesehen? Neue Antworten auf diese Fragen werden in der Reaktorsicherheitsforschung erarbeitet. Dass Forschungsaktivitäten im Bereich hypothetischer Ereignisse mit äußerst geringer Eintrittswahrscheinlichkeit eine Sicherheitskultur auf hohem Niveau unterstützen und weitere Verbesserungsvorschläge auch für bestehende Anlagen ermöglichen, belegen Ergebnisse einer Forschungsarbeit zur Rückhaltbarkeit von Kernschmelze im Reaktordruckbehälter.

Some facts about the spectrum of a PT-symmetric quantum mechanical (PTSQM) toy model with potential V(x)=Gx²(ix)^ν in a box x∈[-L,L] are presented for the parameter region ν∈[-2,0]. The corresponding Hamiltonian is selfadjoint in an appropriately chosen Krein space and for ν=-1 the spectral problem maps into that of the hydrodynamic Squire equation. It is shown that in the limit L→∞ a spectral singularity occurs and that the PTSQM ⇄ Squire mapping can be interpreted as a special type of strong-coupling ⇄ weak-coupling (UV-IR) duality. Finally, the system behavior in the vicinity of a spectral triple point is sketched.
partially based on:
J. Math. Phys. 46, (2005), 063504, math-ph/0501069.
Czech. J. Phys. 55, (2005), 1099-1106, math-ph/0506021.

The presentation comprises an introduction in the theory of diffuse scattering, experimental conditions, classical technique and difference technique, LAXS and HEXS. Several typical examples and potential applications will be discussed.

An overview on EXAFS on applications on actinide structure investigation in solution will be given.

Nano-catalysts made from palladium and other noble metals promise to accelerate chemical reactions even at low temperatures. Critical for the efficiency of such nano-catalysts is a perfect control of their cluster-size. By using the surface protein layer (so-called S-layer) of a bacterium, particles with a uniform size distribution of 50 to 80 Pd atoms can be generated. For the first time, the bonding sites between the metal and the S-layer protein have been characterized. Hereby, the prerequisite is given to manipulate this protein by genetic engineering enabling the design of materials with new optic, magnetic and catalytic properties.
The uranium uptake mechanism were investigated by EXAFS performed at the Rossendorf Beamline. The measurements revealed that the purified S-layer proteins of this bacterium coordinate uranium through phosphate groups of phosphorylated serine and threonine in a monodentate mode as well as through carboxyl groups of aspartic and glutamic acids in a bidentate mode.
The heavy metal binding capacity of the S-layer led to the idea to use it as template for the formation of Pd nanoclusters. Within the pores of the S-layer, isolated from vegetative bacteria, Pd(II) solutions are reduced to metallic palladium by the use of hydrogen.
In order to investigate the metal-protein interactions and their impact on the secondary structure, a solution of Pd(II) ions has been sorbed on the S-layer matrix. The combination of Fourier transform infrared spectroscopy and EXAFS spectroscopy revealed that the surface Pd(II) is predominantly coordinated by aspartic and glutamic residues through 4 nitrogen and oxygen atoms at a distance of 2.01 Å. In contrast to U(VI), that binds to carboxyl and phosphate groups, Pd(II) binds exclusively to the carboxyl groups of the S-layer. The topology of nitrogen- and carboxyl-bearing side chains appears to mediate the binding of heavy metals to aspartic and glutamic acids. These side chains are thus targets for the design of engineered S-layer based nanoclusters.

The effect of flash lamp annealing applied to ZnO single crystals implanted with 3.6 at. % Fe has been studied. For intermediate light power, the implantation induced surface defects could be annealed without creation of secondary phases within the implanted region. At the same annealing temperatures, however, ion beam induced open volume defects start to increase in size. Recrystallization is initiated for the highest light power applied, i.e. the ion beam induced lattice disorder reflected by the minimum channelling yield of Rutherford backscattering spectroscopy decreases from 76 % to 46 % and the open volume defects are annealed. At the same time, the Fe3+ fraction increases at the cost of the Fe2+ states. Weak ferromagnetic properties are induced, that are mainly associated with nanoparticles

First results on a perturbation theory for α²-dynamos with non-constant spherically symmetric α-profiles are presented. The basics of the mathematical technique is demonstrated on a simplified model with idealized boundary conditions (BCs). Such BCs allow for a full semi-analytical treatment of the problem due to the selfadjointness of the dynamo operator in a so called Krein space --- a Hilbert space with an additional indefinite metric structure.
Starting point of the consideration is the model with constant α-profile α₀ which is exactly solvable. The eigenvalues λ of such a model form a mesh-like branch structure in the (α₀,Re λ)-plane. The nodes of this mesh (the intersection points of the branches) are double semi-simple eigenvalues (diabolical points) of algebraic and geometric multiplicity 2.
A Krein space related perturbation theory as well as a Galerkin technique for the numerical treatment of inhomogeneous perturbations of the α-profile have been developed. With the help of these tools, a very pronounced α-resonance pattern has been found in the deformations of the spectral mesh as well as in the unfolding of the diabolical points. The selection rules of this resonance pattern are defined by the Fourier coefficients of the perturbations leading to a strong correspondence between the characteristic length scale of the α-perturbations and the decay rates of the coherently induced field excitations. Such correlations will exist also in models with realistic BCs and may provide a qualitative explanation for some specifics of field reversal processes --- supporting corresponding numerical simulations on more realistic dynamo setups.
Furthermore, an estimation technique has been developed for obtaining optimal α-profiles for which α²-dynamos can become overcritical in oscillatory regimes. This basic technique is demonstrated explicitly for a simplified monopole (l=0) model, where it leads to a bound on the Fourier components of the α-profile. The capability of the used Galerkin approach is demonstrated in extending the strength of the α-perturbations from weakly perturbed regimes to strongly perturbed ones.
Extensions of the presented techniques to spherically symmetric α²-dynamos with realistic boundary conditions are in preparation.

A parameter study of a hypothetical boron dilution event during the work of the RHRS was performed. Based on a validated coolant mixing model for the lower plenum of the RPV, realistic boron concentration curves at the inlet into each fuel assembly were obtained and used for a number of stationary and transient core calculations. For the generic core loading pattern used in the calculations, in the stationary calcu-lations recriticality is reached for slug volumes of about 8 m3 if the realistic core inlet boron concentration distribution is used. Transient core calculations from 8 to the maximum initial slug volume of 15 m3 showed, that the maximum calculated fuel and cladding temperature values are below critical values. Although in all calculations local coolant boiling occurs over several tenths of seconds, the integrity of the fuel is always ensured according to the calculation results.

Light emitting pn-diodes were fabricated on a 5.8 µm thick n-type Si device layer of a silicon-on-insulator (SOI) wafer using standard silicon technology and boron implantation. The thickness of the Si device layer was reduced to 1.3 µm, corresponding to a 4λ-cavity for λ = 1150nm light. Electroluminescence spectra of these low Q-factor microcavities are presented. Addition of Si/SiO₂ Bragg reflectors on the top and bottom of the device (3.5 and 5.5 pairs, respectively) is predicted to lead to spectral emission enhancement by ∼270.

We consider two models of spherically-symmetric MHD α²-dynamos --- one with idealized boundary conditions (BCs) and one with physically realistic BCs. As it has been shown in our previous work, the eigenvalues λ of a model with idealized BCs and constant α-profile α₀ are linear functions of α₀ and form a mesh in the (α₀,Re λ)-plane. The nodes of the spectral mesh correspond to double-degenerate eigenvalues of algebraic and geometric multiplicity 2 (diabolical points). It was found that perturbations of the constant α-profile lead to a resonant unfolding of the diabolical points with selection rules of the resonant unfolding defined by the Fourier coefficients of the perturbations. In the present contribution we present new exact results on the spectrum of the model with physically realistic BCs and constant α₀. For non-degenerate (simple) eigenvalues perturbation gradients are found at any particular α₀. We present a detailed study of the spectral behavior of the α²-dynamo operator over a family of homotopic deformations of the BCs between idealized ones and physically realistic ones. Furthermore, we demonstrate that although the spectral singularities are lifted, a memory about their locations remains deeply imprinted in the homotopic family of the spectral deformations due to a hidden underlying invariance.

The single-pion production reactions pp → dπ+, pp → npπ+ and pp → ppπ0 were measured at a beam momentum of 0.95GeV/c ( T p ≈ 400MeV) using the short version of the COSY-TOF spectrometer. The implementation of a central calorimeter provided particle identification, energy determination and neutron detection in addition to time-of-flight and angle measurements. Thus, all pion production channels were recorded with 1-4 overconstraints. The total and differential cross-sections obtained are compared to previous data and theoretical calculations. Main emphasis is put on the discussion of the ppπ0 channel, where we obtain angular distributions different from previous experimental results, however, partly in good agreement with recent phenomenological and theoretical predictions. In particular, we observe very large anisotropies for the π0 angular distributions in the kinematical region of small relative proton momenta revealing there a dominance of proton spinflip transitions associated with π0 s and d partial waves and emphasizing the important role of π0 d-waves.

The reaction dp → pppπ- has been studied in a kinematically complete experiment at a single beam momentum p_d =1.85 GeV/c (T = 759MeV). All four ejectiles have been detected in the large-acceptance time-of-flight spectrometer COSY-TOF. We analyzed the data along the lines of the spectator model as a means to isolate the quasi-free np → pppπ- reaction. The spectator proton was identified by its momentum and flight direction thus yielding access to the associated Fermi motion of the bound neutron. A comparison is carried out with Monte Carlo simulations based on two different parameterizations of the deuteron wave function. Up to a Fermi momentum of roughly 150MeV/c no significant deviations between experimental and simulated data of various observables were found from which we conclude that the deuteron can indeed be taken as a valid substitute for the neutron.

This paper reports on to the realization of piezoresistive cantilever-Arrays used in scanning probe microscopy (SPM). Sensors for the SPM are peculiar microsystems since the combination of physical and microtechnological principles allows to gain an insight into the material science at nanoscale. Moreover SPM technology is opening new horizons in fundamental research and gives a chance to employ new interaction principles for the realization of new sensors and sensor arrays. Physical, biological, and chemical values and interactions can effectively be detected and analyzed using cantilevers, where the nanomechanical interactions can be transformed into an electric signal. The basic issues for the realization of a complete system of self-actuated, piezoresistive cantilever arrays are described.

Wire-mesh sensors deliver sequences of instantaneous, two-dimensional gas fraction distributions from a measuring cross-section. The spatial and temporal resolutions are high enough to reflect individual bubbles in much more than one measuring frame during their passage through the sensor plane. The bubbles can therefore be detected by a pattern recognition method based on the identifications of connected areas of gas-filled elements in the array of local instantaneous gas fractions, available as a function of the lateral co-ordinates x,y and as function of time. Algorithms were presented in earlier publications, which are based on a recursive fill procedure that assigns individual bubble numbers to the elements of the gas fraction array. This procedure has to rely on a threshold for the cancellation of the recursive fill, because the gas fraction data are affected by noise. The choice of the correct threshold is difficult, since a too high gas fraction threshold leads to unrealistic bubble fragmentation, while a too low threshold provokes unrealistic unification of bubbles. In previous papers an optimum approach was found by introducing a differential threshold determined for each bubble individually from the maximum gas fraction inside the given bubble to identify the cores of the bubbles. This is combined with an agglomeration step, where elements with a gas fraction below the threshold are assigned to already existing bubble cores, if these elements were not yet assigned to a bubble in the recursive fill step.
In the present paper, the algorithm will be analysed by applying it to synthetic measuring data, which is generated by placing bubbles of known geometrical parameters into the discretization measuring grid defined by the wire-mesh geometry. The discretization is performed with due care to reflect the fact that the gas-liquid interface at the periphery of the bubbles crosses control volumes of the measuring grid, producing local instantaneous void fractions of intermediate values. The synthetic signals are furthermore superposed by synthetic white noise. It is shown that the original bubble recognition algorithm needs to be improved in certain cases: (a) Unrealistic fragmentation in axial (time) direction may occur, when bubbles cross the sensor plane with a low velocity. (b) non-realistic coalescence becomes dominating at very high gas fractions, where bubbles of complex shape occur. Different improvements were tested. Unrealistic coalescence is avoided by introducing a criterion to terminate the recursive fill algorithm, which are based on the local gradient of the gas fraction. A second approach relies on a repair algorithm, which unites unrealistic fragments in an additional processing step after the preliminary bubble recognition. This repair algorithm takes benefit from a-priory knowledge to distinguish realistic close neighbour bubbles from unrealistic bubble fragments divided by an early truncation of the bubble recognition. After the check against synthetic bubbles, the algorithms are applied to real measuring data from gas-liquid flows in vertical pipes and the results obtained by the different algorithms are compared.

A new class of semi-analytically solvable MHD α²-dynamos is found based on a global diagonalization of the matrix part of the dynamo differential operator. Close parallels to SUSY QM are used to relate these models to the Dirac equation and to extract non-numerical information about the dynamo spectrum.

This study carried out at the Institut de Radioprotection et de Sûreté Nucléaire (IRSN) concerns the bubbly flow numerical simulation. One of the determining features of the two-phase flow is the topology of the flow. Local interfacial area concentration, say ai, allows to determine the exchange surface for momentum, heat and mass transfers between liquid and vapor. In the case of bubbly flow the size of the inclusion, say D, (through the non-dimensional Eötvös number) determines essential liquidvapor momentum transfers such as the lift force (e.g. (Tomiyama et al. 1995)). The corresponding fields ai and D are functions of history, flow conditions, as well as local events such as coalescence, break-up and phase change. This justifies to model their evolution thanks to additional transport equations (in addition to momentum, mass and energy balance equations). Several approaches can then be distinguished, namely the population balance (Coulaloglou and Tavlarides 1977), the two-group interfacial area transport (Fu and Ishii 2002) or the moment densities (Kamp et al. 2001). The purpose of the present study is to examine the ability of the NEPTUNE_CFD code to predict bubble size distribution in complex flow configurations.
A series of experiments performed at FZD in the frame of the TOPFLOW project allows to determine the local structure of the two-phase flow including the bubble size local distribution. We focus more particularly on bubbly air-water flows around an asymmetric obstacle in the section of a vertical pipe (see (Prasser et al. 2006)). The presence of the obstacle induces a pronounced three-dimensional effect as well as coalescence events. We perform numerical simulations with the NEPTUNE_CFD code of these experiments. The NEPTUNE_CFD code (see (Guelfi et al. 2005)) is based on the two-fluid model formulation. It is developed in the frame of a research program supported by EDF, CEA, IRSN and AREVA_NP. In the present study, two different levels of description of the bubble size distribution in space and time are considered. At the first level of description, the bubble size distribution is determined thanks to an interfacial area equation allowing to define locally a single bubble size (monodisperse flow). At the second level we consider locally a spectrum of bubble sizes (polydisperse flow) with the help of a moment densities approach. We incorporate the model within NEPTUNE_CFD and present the resulting gain in accuracy of the simulation. Perspectives concerning improvement of the numerical modelling of bubble size distribution are discussed.

In this paper, a correlation between structural and magnetic properties of Fe-implanted ZnO is presented. High fluence Fe+ implantation into ZnO leads to the formation of superparamagnetic α-Fe nanoparticles. High vacuum annealing at 823 K results in the growth of α-Fe particles, but the annealing at 1073 K oxidizes the majority of the Fe nanoparticles. After a long term annealing at 1073 K, crystallographically oriented ZnFe2O4 nanoparticles are formed inside ZnO with the orientation relationship of ZnFe2O4(1 1 1)[1 1 0]//ZnO(0 0 0 1)[11 2 0]. These ZnFe2O4 nanoparticles show a hysteretic behaviour upon magnetization reversal at 5 K.

The copper(I)-mediated 1,3 dipolar [3+2]cycloaddition between terminal alkynes and azides, also referred to as click-chemistry, was used to synthesize a ¹⁸F-labeled neurotensin(8-13) (NT(8-13)). 4-[¹⁸F]Fluoro-N-(prop-2-ynyl)benzamide [¹⁸F]1 as novel terminal alkyne building block could successfully be coupled with azide-functionalized NT(8-13) 4 to give the corresponding ¹⁸F-labeled NT(8-13) derivative [¹⁸F]5 product in 66% yield as determined by radio-HPLC. The in vitro binding affinity of 18F-labeled NT(8-13) derivative [¹⁸F]5 was determined to be 66 nM.

Investigations into the formation of intrinsic colloids and pseudocolloids of uranium(IV) were performed. Coulometric titrations of strongly acidic U(IV) solutions in HClO4/NaClO4 medium were carried out in order to find the pH of first colloid formation. Laser-induced breakdown detection (LIBD) was applied for the detection of traces of uranium colloids as the pH was increased. The pH values at the onset of colloid formation were used for thermodynamic calculations aimed at determining the solubility products of crystalline and amorphous uranium dioxide. Furthermore, the UO2·xH2O(am) colloids were investigated for their colloidal stability. Zeta potentials of ≥ 30 mV were found for pH values of less than 4. The point of zero charge was found at pH ~ 6.9. Colloidal suspensions of 1 mMol/L UO2·xH2O(am) at a pH value of 2.5 proved to be stable over > 1.5 years. The interaction of the forming UO2·xH2O(am) colloids with other colloid-forming species was tested. Therefore, coulometric titrations of U(IV) solutions in the presence of (a) dissolved Al(III) and (b) dissolved silicate were carried out. The presence of Al(III) does not significantly influence the formation of the UO2·xH2O(am) colloids, and the presence of U(IV) does not significantly influence the behaviour of Al(III). Also silicate does not significantly influence the pH of UO2·xH2O(am) colloid formation. However, the presence of U(IV) significantly influences the behaviour of the silicate (formation of pseudocolloids). The nature of the interaction between the silicate and the U(IV) is not yet known (adsorption? formation of a coffinite precursor?). EXAFS experiments to elucidate the local structure around the U(IV) atoms in the pseudocolloids are under preparation.

Gallium forms complexes of the general formula [Ga(NS₃)NHR₂], where NS₃ is the tripodal ligand tris(2-mercaptoethyl) amine and secondary amines (NHR₂) are co-ligands. Structure determinations reveal trigonal-bipyramidal structure of the mononuclear species and the tendency of solvent-coordinated species [Ga(NS₃)solv] (solv: water, methanol) to condensate to trinuclear species. Challenge experiments with the plasma protein transferrin, performed with the respective Ga-68 complexes, show enhanced stability of the aminederived species [Ga(NS₃)NHR₂] with piperidine and imidazole derivatives as the most stable complexes.

Theoretical approaches used in investigations of relativistic effects in high energy lepton and hadron collisions with few nucleon systems are analyzed. The Bethe-Salpeter formalism for describing interacting systems of two spinor particles both in the continuum and bound state is described in detail. Special attention is paid to partial expansions taking into account the analytic properties of Bethe-Salpeter amplitudes and unitary transformations correlating different representations of partial amplitudes. Mathematical methods of numerical solution of equations are considered. Results of calculation of relativistic corrections and effects of interactions in the final state in particular reactions with the deuteron, namely, inelastic pD backward scattering and in reactions of deuteron break-up with production of correlated pairs, are presented.

We analyze the possibility to produce an intermediate Tp via a KN to Tp formation process in gamma D to pK^-X (X=nK⁺,pK⁰) reactions at some specific kinematical conditions, in which a pK^- pair is knocked out in the forward direction and its invariant mass is close to the mass of Ls (Ls equiv Lambda(1520)). The Theta⁺ signal may appear in the [gamma D,pK^-] missing mass distribution. The ratio of the signal (cross section at the Theta⁺ peak position) to the smooth background processes varies from 0.7 to 2.5 depending on the spin and parity of Tp, and it decreases correspondingly if the pK^- invariant mass is outside of the Ls-resonance region. We analyze the recent CLAS search for the Tp in the gamma D to pK^-nK⁺ reaction and show that the conditions of this experiment greatly reduce the Tp formation process making it difficult to extract a Tp peak from the data.

Dalitz decays of omega and rho mesons, omega to pi⁰gamma^* topi⁰ e⁺e^- and rho⁰ to pi⁰gamma^* to pi⁰ e⁺e^-, produced in pp collisions are calculated within a covariant effective meson-nucleon theory.
We argue that the omega transition form factor F_{omega to pi⁰gamma^*} is experimentally accessible in a fairly model independent way in the reaction pp to pp pi⁰ e⁺ e^- for invariant masses of the pi⁰ e⁺ e^- subsystem near the omega pole.
Numerical results are presented for the intermediate energy kinematics of envisaged HADES experiments.

This work is part of efforts to develop chelating agents for stable binding and easy conjugation of Re-188 to biologically interesting structures. Starting from the high in vivo stability of [¹⁸⁸ReO(DMSA)₂]^- we want to exploit this coordination system for the design of ¹⁸⁸ReO(V) chelates which are stable towards re-oxidation to perrhenate under conditions of radiopharmaceutical procedures. Therefore a new type of tetradentate ligand has been synthesized by bridging two molecules on N-N'-diisobutyl-2,3-dimercaptosuccinamide with N-(3-aminopropyl)propane-1,3diamine. The resulting stereoisomeric tetrathiolato S₄ligand forms anionic five-coordinated oxorhenium(V) complexes by ligand exchange reaction of NBu₄[ReOCl₄]in methanol. Without addition of base the compounds will be isolated as "betain", [ReO(S₄)], with the protonated nitrogen of the bridge as a internal "counter ion".
Two representatives have been characterized in solid state and found to adopt the expected square-pyramidal coordination geometry. The equatorial plane is formed by four thiolate sulfur atoms, whereas the oxygen occupies the apical position. The orientation of the metal oxo group is exo in relation to the carbamido groups in both isomers. The complexes are stereoisomeric regarding the junction of the triamine chain. The Re-188 labelling procedure runs fast, in good yields and under mild conditions, making the new complexes interesting as access to stable Re-188 radiotherapeutics.

T. Heinrich, W. Kraus, H.-J. Pietzsch et al. Inorg. Chem., 44, 9930-9937 (2005).

Vortrag über Lumineszenzeigenschaften des Urans in verschiedenen Oxidationsstufen

Substantial evidence has accumulated that the myeloperoxidase (MPO)/hydrogen peroxide/hypochlorite system of phagocytes plays a critical role not only in antimicrobial defence but also in chronic inflammatory conditions like atherosclerosis. Oxidation of low-density lipoproteins (LDL) by hypochlorite (OCl-LDL) results in physico-chemical modifications of both the protein and lipid moiety of the lipoprotein molecule. Following oxidation OCl-LDL display a number of proatherogenic and proinflammatory properties including stimulation of phagocyte oxidant generation, induction of leukocyte degranulation, and increase of phagocyte adhesion to endothelial cells. Importantly, the class B scavenger receptors CD36 and SR-BI are receptors for OCl-LDL. This fact may explain the high uptake of OCl-LDL in macrophages, leading to the formation of foam cells. Our investigations revealed that OCl-LDL upregulates the gene expression of CD36 and PPAR in macrophages dose- and time-dependently while modulating SR-BI expression differently in dependence on incubation conditions. The antiatherogenic properties of high-density lipoproteins (HDL) are suggested to be mainly associated with its SR-BI-mediated reverse cholesterol transport. In addition we could demonstrate that HDL possesses anti-inflammatory actions by inhibiting OCl-LDL-induced increase in phagocyte respiratory burst and adhesion to endothelial cells. The protective role of HDL was substantially attenuated when HDL apolipoproteins were oxidized by hypochlorite. Our in vitro data show that hypochlorite-oxidized lipoproteins could mimic fundamental atherogenic and inflammatory processes therefore underlying the potential role of hypochlorite oxidation as pathogenetic factor in vivo.

Growing evidence indicates that diabetes mellitus is accompanied by oxidative stress. In addition to lipids and nucleic acids, proteins also undergo oxidation. Diabetic patients have several groups of oxidatively modified proteins, i.e., advanced glycation end-products, carbonylated proteins, and advanced oxidation protein products, in the circulation. Oxidized proteins have also been detected in tissues of animals with experimental diabetes. Oxidative modifications of mitochondrial proteins are blunted in diabetic conditions. Of special interest is the oxidation of apolipoprotein B-100, the structural protein of low density lipoproteins. Oxidatively modified apolipoprotein B-100 molecules had been detected in atherosclerotic lesions as well as in the circulation. Oxidatively altered proteins lead to vascular damage. Increased oxidative stress was also observed in gestational diabetes. Protein oxidation plays a major role in the development of diabetes complications and has been implicated in the pathogenesis of diabetic nephropathy, neuropathy and retinopathy. In diabetic nephropathy which develops as a result of complex interplay of hemodynamic and metabolic factors, oxidative protein modifications contribute to albuminuria, mesangial expansion, glomerulosclerosis and tubulo-interstitial fibrosis. There is also strong experimental evidence that morphological abnormalities of diabetic retinopathy, such as pericyte dropout, formation of acellular capillaries, are associated with non-enzymatic glycosylation (glycation) and accumulation of advanced glycation end-products. Protein oxidation also takes place in the lens and plays a central role in the development of cataract. Growing evidence implicates advanced protein glycoxidation and lipoxidation in the pathogenesis of both somatic and autonomic diabetic neuropathy, and, in particular, motor and sensory nerve conduction deficits, neurovascular dysfunction, diabetic neuropathic pain and loss of sensory function, and morphological abnormalities characteristic for peripheral and autonomic neuropathy.

Oxidative modification of LDL apolipoprotein (apo) B-100 by myeloperoxidase-generated hypochlorous acid (HOCl) is regarded as a crucial event in atherogenesis. Exemplarily, HOCl-modified LDL (OCl-LDL) apoB-100 has been shown to be present in the human aortic vessel wall from various stages of atherosclerotic lesion evolution. On the other hand, data concerning the role of circulating OCl-LDL in the development of atherosclerosis are scarce. One reason for this is the shortage of methods for direct assessment of metabolism of oxidatively modified LDL in vivo. We report an improved methodology for radiolabeling of both native LDL (nLDL) and HOCl-LDL with the positron-emitter fluorine-18 (¹⁸F) by N-succinimidyl 4-[¹⁸F]fluorobenzoate ([¹⁸F]SFB) and the use of [¹⁸F]fluorobenzoylated LDL particles in dynamic positron emission tomography (PET) studies in rats. As model reactions, nLDL were modified in vitro by 3 mM NaOCl. For radiolabeling, pools of chemically and biochemically well characterized human nLDL and OCl-LDL were used. Preparation of [¹⁸F]SFB was achieved by module-assisted synthesis within 68 min with radiochemical yields of 36±2% (corrected for decay) and purity of >95%. LDL labeling with [¹⁸F]SFB resulted in radiochemical yield of 30±10% (nLDL; corrected for decay) and 10±5% (OCl-LDL), respectively, with specific radioactivity of 50-400 GBq/µmol. Radiolabeling of native and modified LDL using [¹⁸F]SFB caused neither additional oxidative structural modifications of LDL lipids and proteins nor alteration of their biological activity and functionality in vitro, respectively. The method was further evaluated with respect to the uptake of [¹⁸F]fluorobenzoylated native and modified LDL particles, respectively, in various human cells. Biodistribution studies in rats revealed high in vivo stability for the [¹⁸F]fluorobenzoylated LDL particles. The metabolic fate of [¹⁸F]fluorobenzoylated nLDL and OCl-LDL particles in vivo was delineated by dynamic PET studies using a dedicated small animal positron emission tomograph. Dynamic PET data demonstrated a significantly enhanced catabolism of OCl-LDL when compared with nLDL. The in vivo distribution and kinetics of both native and modified LDL particles in the rat correlated well with the anatomical localization of LDL receptors and scavenger receptors. In conclusion, [¹⁸F]SFB-labeling of LDL and the use of small animal PET provide a valuable tool to discriminate the kinetics and the metabolic fate of both native and oxidatively modified LDL in animal models in vivo.