Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

"Online First" included
Without submitted and only approved publications
Only approved publications

34122 Publications

The sorption processes of Np(V) and U(VI) onto metal oxide phases. The formation of sorption complexes and mechanistic aspects studied by in situ ATR FT-IR spectroscopy

Foerstendorf, H.; Müller, K.; Heim, K.

The migration behaviour of actinide ions in the geosphere is generally influenced by sorption processes in aqueous media. These processes occurring at solid/liquid interfaces can be monitored by in situ Attenuated Total Reflection Fourier-transform Infrared (ATR FT-IR) spectroscopy providing structural information on a molecular level.[1]
In this work, the sorption of neptunium(V) onto metal oxides was investigated for the first time. From the Np(V) sorption studies on the metal oxides, stable surface species of NpO2+ are derived. The type of the sorbed species can be elucidated by a spectral shift (~ 30 cm−1) to lower wavenumbers of the antisymmetric stretching vibration υ3(NpO2+) compared to the aqueous species suggesting an inner-sphere complexation. Outer-sphere complexation is found to play a minor role due to the pH independence of the sorption species throughout the pH range 4 – 7.6. The comparative spectroscopic experiments of Np(V) sorption onto TiO2, SiO2 and ZnO indicate structurally similar bidentate surface complexes.[2]
A detailed insight into the molecular mechanisms occurring during the formation of ternary actinide complexes at the solid/liquid interface is provided upon formation of uranyl carbonato complexes on ferrihydrite (Fh). The influence of the presence of atmospheric carbon dioxide during the sorption processes of the actinide ions was studied by sorption experiments which were carried out under inert gas conditions and in an ambient atmosphere. From the results, the formation of bidentate [Fh•••UO2•••O2CO] complexes can be derived under mildly acid conditions which is in agreement from recent EXAFS results obtained from batch samples.[3]
Furthermore, experiments with 13C labelled carbonate provide an unequivocal assignment of the spectral features reflecting the structural alterations of the carbonate ions upon sorption of uranyl cations onto Fh. From these assignments, the formation of the ternary uranyl complexes can be described at a molecular level.

References
[1] Lefèvre, G. (2004) Adv. Colloid Interface Sci. 107, 109-123.
[2] Müller, K. et al. (2009) Environ. Sci. Technol., in press.
[3] Rossberg, A. et al. (2009) Environ. Sci. Technol. 43, 1400-1406.

  • Contribution to proceedings
    16th Radiochemical Conference, 18.-23.04.2010, Marianske Lazne, Czech Republic
    Chemicke listy, Vol. 104, Praha: Czech Chemical Society, 0009-2770, s178-s178
  • Lecture (Conference)
    RadChem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Mariánske Lázne, Czech Republic

Permalink: https://www.hzdr.de/publications/Publ-13203
Publ.-Id: 13203


Enhancement Of Electrical And Chemical Surface Properties Of Titanium And Iron-Carbon Alloys Irradiated With A Low-Energy Intense Pulsed Electron Beam

in Russian

Markov, A. B.; Reuther, H.; Shevchenko, N.; Kolitsch, A.

Processes leading to homogenization of chemical and phase composition of near-surface layers materials made from titanium and iron-carbon alloys under irradiation of a low energy intense pulsed electron beam have been investigated. It has been shown that preliminary heating leads to appearance of a more homogeneous chemical composition of surface alloy. It has been determined that an electron-beam polishing took place during irradiation. Irradiation results in dissolution of secondary phase inclusions, decreasing of roughness, and as a result in the enhancement of electrical and chemical surface properties of titanium and iron-carbon alloys.

  • Contribution to proceedings
    19th Int. Crimean Conference Microwave & Telecommunication Technology, 14.-18.09.2009, Sevastopol, Ukraine
    Enhancement Of Electrical And Chemical Surface Properties Of Titanium And Iron-Carbon Alloys Irradiated With A Low-Energy Intense Pulsed Electron Beam, 978-966-335-244-594 2., 593-594

Permalink: https://www.hzdr.de/publications/Publ-13202
Publ.-Id: 13202


Phase-sensitive terahertz spectroscopy with BWOs in reflection mode

Pronin, A. V.; Goncharov, Y. G.; Fischer, T.; Wosnitza, J.

We report on a method, which allows accurate measurements of complex reflection coefficient of a solid at frequencies 1 to 50 cm-1 (30 GHz - 1.5 THz). Backward-wave oscillators (BWOs) are used as sources of monochromatic coherent radiation, tunable in frequency. The amplitude of the complex reflection (the reflectivity) is measured in a standard way, while the phase shift, introduced by the reflection from the sample surface, is measured using a polarizing Michelson interferometer. This method is particular useful for not-transparent samples (such as metals, superconductors, etc.), where phase-sensitive transmission measurements are not possible.
The method requires no Kramers-Kronig transformation in order to extract the sample's electrodynamic properties (such as complex dielectric function or complex conductivity). Another area of application of this method is the study of magnetic materials with complex dynamic permeability different from unity at the measurement frequencies (for example, metamaterials). Measuring both, the phase-sensitive transmission and the phase-sensitive reflection, would allow a straight-forward model-independent determination of the dielectric permittivity and magnetic permeability of such materials.

  • Poster
    The 34th International Conference on Infrared, Millimeter, and Terahertz Waves, 21.-25.09.2009, Busan, Korea

Permalink: https://www.hzdr.de/publications/Publ-13201
Publ.-Id: 13201


Memory effect of Mn5Ge3 nanomagnets embedded inside a Mn-diluted Ge matrix

Zhou, S.; Shalimov, A.; Potzger, K.; Helm, M.; Fassbender, J.; Schmidt, H.

Crystalline Mn5Ge3 nanomagnets are formed inside a Mn-diluted Ge matrix using Mn ion implantation. A temperature-dependent memory effect and slow magnetic relaxation are observed below the superparamagnetic blocking temperature of Mn5Ge3. Our findings corroborate that the observed spin-glass-like features are caused by the size distribution of Mn5Ge3 nanomagnets, rather than by the inter-particle interaction through the Mn-diluted Ge matrix.

Permalink: https://www.hzdr.de/publications/Publ-13200
Publ.-Id: 13200


Bruchmechanische Werkstoffcharakterisierung zur Überwachung der Neutronenversprödung von Reaktordruckbehältern für den Langzeitbetrieb von Kernkraftwerken

Zurbuchen, C.; Viehrig, H.-W.

Die Schweizer Richtlinie HSK-AN-425 dient der bruchmechanische Werkstoffcharakterisierung zur Überwachung der Neutronenversprödung von Reaktordruckbehältern für den Langzeitbetrieb von Kernkraftwerken. Eine Besonderheit ist, dass nicht quasistatische, sondern dynamische Bruchzähigkeitskennwerte ermittelt werden. Die Richtlinie deckt den gesamten Bereich der Zähigkeit ferritischer Stähle ab, also vom instabilen Spaltbruch in der Tieflage (tiefe Temperaturen) bis zum duktilen Reissen in der Hochlage (hohe Temperaturen) und dem dazwischen liegenden Bereich des Steilabfalls der Zähigkeit.
Ziel des Forschungsprojektes HSK-AN-6305 war, die zentralen Elemente der neuen Richtlinie HSK-AN-425 Rev. 5 durch experimentelle Überprüfung an vergleichbaren Werkstoffen aus dem RDB Biblis C zu validieren (Einfluss der Risslänge, Fortsetzung der MC im oberen ZSÜ-Bereich). Allfällige Schwachstellen der Richtlinie HSK-AN-425 sind zu korrigieren, bevor sie in der Überwachung der Kernanlagen freigegeben werden kann. Der Einfluss der Probendicke und der Probenart auf die quasistatische MC-Referenztemperatur T0 nach ASTM E 1921 sowie auf die dynamische MC-Referenztemperatur T0d nach HSK-AN-425 ist zu bestimmen (Übertragbarkeit der Ergebnisse auf Bauteile und Komponenten), und ob bei den Bruchmechanikproben der herkömmliche Ermüdungsanriss durch EDM-Kerben ersetzbar ist.
In dieser Publikation werden die Ergebnisse des Forschungsprojektes HSK-AN-6305 ausführlich vorgestellt.

Keywords: fracture mechanics; quasistatic; dynamic; Master Curve; crack growth resistance curve; R curve; ASTM E 1921; ASTM E 1820; NM method; HSK-AN-425; HSK AN 425; stretch zone

  • Article, self-published (no contribution to HZDR-Annual report)
    Forschungszentrum Rossendorf 2009
    FZD\FWS\2009\07
    166 Seiten
    ISSN: 1437-322X

Permalink: https://www.hzdr.de/publications/Publ-13199
Publ.-Id: 13199


Bruchmechanische Werkstoffcharakterisierung zur Überwachung der Neutronenversprödung von Reaktordruckbehältern für den Langzeitbetrieb von Kernkraftwerken- Kurzfassung

Zurbuchen, C.

Die Schweizer Richtlinie HSK-AN-425 dient der bruchmechanische Werkstoffcharakterisierung zur Überwachung der Neutronenversprödung von Reaktordruckbehältern für den Langzeitbetrieb von Kernkraftwerken. Eine Besonderheit ist, dass nicht quasistatische, sondern dynamische Bruchzähigkeitskennwerte ermittelt werden. Die Richtlinie deckt den gesamten Bereich der Zähigkeit ferritischer Stähle ab, also vom instabilen Spaltbruch in der Tieflage (tiefe Temperaturen) bis zum duktilen Reissen in der Hochlage (hohe Temperaturen) und dem dazwischen liegenden Bereich des Steilabfalls der Zähigkeit.
Ziel des Forschungsprojektes HSK-AN-6305 war, die zentralen Elemente der neuen Richtlinie HSK-AN-425 Rev. 5 durch experimentelle Überprüfung an vergleichbaren Werkstoffen aus dem RDB Biblis C zu validieren (Einfluss der Risslänge, Fortsetzung der MC im oberen ZSÜ-Bereich). Allfällige Schwachstellen der Richtlinie HSK-AN-425 sind zu korrigieren, bevor sie in der Überwachung der Kernanlagen freigegeben werden kann. Der Einfluss der Probendicke und der Probenart auf die MC-Referenztemperatur T0 ist zu bestimmen (Übertragbarkeit der Ergebnisse auf Bauteile und Komponenten), und ob bei den Bruchmechanikproben der herkömmliche Ermüdungsanriss durch EDM-Kerben ersetzbar ist.
In dieser Publikation werden die Hauptergebnisse des Forschungsprojektes HSK-AN-6305 vorgestellt.

Keywords: fracture mechanics; quasistatic; dynamic; Master Curve; crack growth resistance curve; R curve; ASTM E 1921; ASTM E 1820; NM method; HSK-AN-425; HSK AN 425; stretch zone

  • Article, self-published (no contribution to HZDR-Annual report)
    Forschungszentrum Rossendorf 2009
    FZD\FWS\2009\08
    16 Seiten
    ISSN: 1437-322X

Permalink: https://www.hzdr.de/publications/Publ-13198
Publ.-Id: 13198


Complexation of U(VI) with Nitrogen and Phosphorous Containing Ligands in Aqueous Solution

Raditzky, B.; Schmeide, K.; Sachs, S.; Bernhard, G.

The long-term safety assessment of nuclear waste disposals requires detailed knowledge of the transport and interaction behavior of actinides within the technical, geotechnical and geological barriers. In the case of accidental release of radionuclides into the surrounding environment, their migration behavior can be effectively influenced by the ambient conditions like pH, temperature, ionic strength and especially the presence of inorganic and organic complexing ligands, e.g. bioligands like humic acids, amino acids or phospholipids. Due to their high complexing capacity towards metal ions these ligands may influence the mobility of actinides.

We studied the U(VI) complexation with nitrogen and phosphorous containing model ligands in order to simulate the functionalities of bioligands. The aim of this work is to determine the influence of various nitrogen and phosphorous containing functional groups on the U(VI) complexation and to evaluate their contribution in comparison to oxygen containing functional groups. As nitrogen containing ligands we used the biologically important substances anthranilic acid (AA) and nicotinic acid (NA). Furthermore, phenylphosphonic acid (PPA) was used as aromatic phosphorous containing ligand.

The complexation studies in aqueous solution were performed as a function of pH using time-resolved laser-induced fluorescence spectroscopy (TRLFS). All ligands show a complex formation with U(VI) under the given experimental conditions ([U(VI)] = 0.05 mM, [ligand] = 0 – 0.5 mM, pH 2-4, I = 0.1 M, T = 25°C). The binding of U(VI) by AA and NA takes place via the carboxylic group of the ligands. It can be concluded, that oxygen containing functional groups dominate the U(VI) complexation in the investigated pH range. The nitrogen functionalities of the ligands play only a subordinate role. AA forms a 1:1 complex, with a corresponding stability constant of log ß11 = 3.14 +/- 0.17 [1]. The formation of 1:1 and 1:2 complexes was detected for the U(VI)-nicotinate system (log ß11 = 3.73 +/- 0.30, log ß12 = 7.46 +/- 0.17 [1]) as well as for the U(VI)-phenylphosphonate system (log ß11 = 3.58 +/- 0.17, log ß12 = 6.81 +/- 0.10). At high U(VI) concentrations (1 mM), a precipitation of the formed complexes was observed for the U(VI) complexation by AA and PPA. The precipitates were analyzed with FT-IR spectroscopy and X-ray diffraction. To study the influence of different functional groups on the complexation of actinides in different oxidation states, comparable complexation studies are performed with Am(III).

References:
[1] B. Raditzky, K. Schmeide, S. Sachs, G. Geipel, G. Bernhard, Polyhedron (2009), doi:10.1016/j.poly.2009.08.010.

  • Contribution to proceedings
    RadChem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Marianske Lazne, Czech Republic
  • Lecture (Conference)
    RadChem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Marianske Lazne, Czech Republic

Permalink: https://www.hzdr.de/publications/Publ-13197
Publ.-Id: 13197


Effect of Ca2+ on the Sorption of Uranium(VI) and Humic Acid on Natural Clay

Joseph, C.; Schmeide, K.; Sachs, S.; Bernhard, G.

In various countries clay is discussed as possible host rock for a nuclear waste repository. The interaction of the clay with actinides, especially U(VI), is the focus of our work. Sorption experiments were performed to estimate the actinide migration in clay formations. Also the influence of humic acid (HA) is investigated. HA are ubiquitously found in natural environments and can interact with e.g. actinides of the nuclear waste. Natural clay contains HA and fulvic acid like organic matter, which can be released from the clay [1]. HA also forms stable colloids. Due to this behavior HA can influence the mobility of actinides, e.g. U(VI), in a nuclear waste repository.

Opalinus clay (OPA) from Mont Terri, Switzerland was studied. Batch sorption experiments were performed in order to determine the sorption ability of U(VI) ([U] = 1x10-6 M) onto OPA in the absence and presence of HA ([HA] = 10 mg/L, 50 mg/L) and of HA in the absence and presence of U(VI) using synthetic OPA pore water (OPAWA, [2], pH 7.6, I = 0.39 M) and NaClO4 (pH 3-10, I = 0.1 M) as background electrolyte. During these studies a large influence of calcite on the sorption behavior of U(VI) and HA was determined. Calcite presents a fraction of 13% in OPA and its ions occur also in the OPAWA ([Ca2+] = 0.03 M, [CO32-] = 5x10-4 M). In OPAWA, U(VI) forms with the ions in solution the neutral aquatic complex Ca2UO2(CO3)3 [3]. This complex dominates the speciation with a fraction of 99%. In sorption experiments it was shown, that this complex adsorbs weakly onto OPA. Normalized to the specific surface area of OPA (BET = 41.6 m2/g) the U(VI) sorption was determined with 0.05 ± 0.002 µg U/m2 clay. In further sorption studies it was shown that HA has no influence on the U(VI) sorption onto OPA. This was also proved by speciation calculations, which showed that also in the presence of HA the Ca2UO2(CO3)3(aq) complex is the dominating species in solution. In order to interpret the sorption data onto OPA, additional zeta potential measurements were performed, where between pH 0 and 7.5 a negative zeta potential for OPA was determined.

The HA sorption onto OPA in OPAWA was determined with 3.57±0.01 µg HA/m2 (10 mg/L) and 17.28±0.15 µg HA/m2 (50 mg/L). In the presence of U(VI), a slight increase of HA sorption (D = 0.3 µg HA/m2) was observed for [HA] = 50 mg/L. Species calculations showed that Ca2+ ions influence also the HA speciation, because Ca2+ is complexed by HA. Ca2+ is present in such a high concentration, that it saturates the binding sites of HA. Thus, only few binding sites, about 0.1% according to speciation calculations, are available for the complexation of U(VI). Consequently, U(VI) and HA have no effect on each other during the sorption studies. These experiments show the large influence of the calcite fraction of the OPA and thus the resulting composition of the OPAWA on the U(VI) and HA sorption. Thus, calcite should be taken into account for the safety case analysis of a nuclear waste repository.

[1] F. Claret et al., Sci. Total Environ. 317, 2003, 189.
[2] F.J. Pearson, PSI Internal Report TM-44-98-07, Switzerland, 1998.
[3] G. Bernhard et al., Radiochim. Acta 89, 2001, 511.

Keywords: opalinus clay; calcium; uranium(VI); humic acid; sorption; pore water; zeta potential

  • Contribution to proceedings
    RadChem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Mariánské Lázne, Czech Republic
  • Lecture (Conference)
    RadChem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Mariánské Lázne, Czech Republic

Permalink: https://www.hzdr.de/publications/Publ-13195
Publ.-Id: 13195


Defect-induced ferromagnetism in crystalline SrTiO3

Potzger, K.; Levin, A. A.; Shalimov, A.; Osten, J.; Meyer, D. C.

Plasma irradiation of high-quality SrTiO3 single crystals leads to room-temperature ferromagnetism. The saturation magnetization is about two orders of magnitude larger than in the pristine material. Structural analysis revealed a polycrystalline layer at the sample surface induced by the plasma irradiation. The results are discussed in the frame of grain-boundary-induced defect ferromagnetism.

Keywords: SrTiO3; defect induced ferromagnetism; plasma irradiation

  • Journal of Magnetism and Magnetic Materials 323(2011)11, 1551-1562
    DOI: 10.1016/j.jmmm.2011.01.018
  • Lecture (Conference)
    75. Jahrestagung der DPG und DPG Frühjahrstagung, 13.-18.03.2011, Dresden, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13194
Publ.-Id: 13194


The influence of magnetic field on the two-dimensional quantum antiferromagnet Cu(tn)Cl2: an intriguing magnetic phase diagram

Orendacova, A.; Cizmar, E.; Sedlakova, L.; Hanko, J.; Kajnakova, M.; Zelenak, V.; Xia, J. S.; Yin, L.; Pajerowski, D. M.; Zvyagin, S. A.; Wosnitza, J.; Orendac, M.; Feher, A.; Meisel, M. W.

Specic heat and magnetic susceptibility measurements, spanning low temperatures (T ≥ 40 mK) and high magnetic elds (B ≤ 14 T), have been performed on Cu(tn)Cl2 (tn = C3H10N2), a two-dimensional (2D) S = 1/2 spatially anisotropic triangular antiferromagnet realized by a square lattice with nearest- neighbor (J=kB = 3 K), frustrating next-nearest-neighbor (0 < J'/J < 0.6), and interlayer (|J''/kB| <3 mK) interactions [1]. The absence of long-range magnetic order down to T = 60 mK in B = 0 and the T2 behavior of the specific heat for T ≤ 0.4 K and B ≥ 0 are considered evidence of 2D magnetic correlations. In fields lower than the saturation field, Bsat = 6.6 T, a specific heat anomaly, appearing near 0.8 K, is interpreted as a Berezinski-Kosterlitz-Thouless (BKT) phase transition. The magnetic phase diagram is remarkably consistent with the theoretical predictions [2], except for the point that Bsat(T -> 0) is shifted to values significantly lower than expected. Potential explanations for this observation will be discussed.

  • Invited lecture (Conferences)
    QFS2009 - International Symposium on Fluids and Solids, 05.-11.08.2009, Evanston, Illinois, USA

Permalink: https://www.hzdr.de/publications/Publ-13193
Publ.-Id: 13193


Teilchenbeschleunigung mit Laserlicht - Chancen für kompakte Strahlungsquellen für medizinische Anwendungen

Schramm, U.

Anwendungsmöglichkeiten laserbeschleunigter Teilchenstrahlen in der Medizin

  • Invited lecture (Conferences)
    17. Jahrestagung der AG Radiochemie / Radiopharmazie, 24.-26.9.2009, Schellerhau, Sachsen, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13192
Publ.-Id: 13192


Polarisationsinduzierte Oberflächenfunktionalität an Ferroelektrika

Eng, L. M.; Grafström, S.; Seifert, G.; Gemming, S.

In structured or self-organized materials spatial confinement effects lead to structure- and interface-controlled modifications of the bulk transport properties. In part, such modifications can be accounted for by a classical master equation approach for the transport of the different charge carrier species. The rather large quantity of parameters, which enter such an approach, can more or less easily be adjusted to the dimensional characteristics, local potential changes at interfaces, and the electronic settings of the system as well as to temperature effects. On the other hand, a microscopically more detailed and mostly parameter-free picture is obtained from a quantum-mechanical treatment on the basis of the density-functional theory. An extension by a Green's function formalism allows the determination and analysis of electronic transport through contacted nanostructures. Examples will be given to demonstrate the applicability of the different approaches for dissipative and hopping transport through a regular array of nanostructures, for a mechanically triggered metal-insulator transition in nanowires, and for the enhanced conductivity at multiferroic domain walls.

Keywords: conduction; conductivity; OFET; FerroFET; transport; SAM; self-assembled; polarization; density-functional

  • Lecture (Conference)
    Abschlusskolloquium des SPP 1157, 21.-22.09.2009, Bonn, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13190
Publ.-Id: 13190


Novel Concepts for Anisotropic Heisenberg Modeling of Multiferroic Oxides

Gemming, S.; Kunze, T.; Numazawa, S.; Schreiber, M.

Thermodynamic equilibration of complex systems like spin glasses or (degenerate) anisotropic spin crystals by numerical methods can be challenging due to the presence of multiple minima on the potential energy surface. This problem becomes pronounced especially at low temperature, where the system remains mainly in few states. We employ the anisotropic Heisenberg model in two dimensions to simulate and analyze the domain formation and the domain structure of multiferroic oxides. In particular, we discuss various techniques to improve the low-temperature equilibration behavior by means of a trigonal antiferromagnet with single-ion anisotropy. Furthermore, we present a localized sampling method for the Metropolis algorithm, which increases the acceptance ratio significantly.

Keywords: Monte-Carlo; Heisenberg; frustrated antiferromagnet; triangular lattice; Metropolis; importance sampling

  • Lecture (Conference)
    45th Symposium on Theoretical Chemisrty, 08.-12.09.2009, Neuss, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13189
Publ.-Id: 13189


First-principles investigation of metal/oxide contacts and related metal/group-IV interfaces

Gemming, S.

Density-functional band-structure calculations have been carried out for two types of material combinations at heterophase boundaries in order to characterise the main influence factors on adhesion.
Strong binding at heterophase interfaces is often related to a favourable and directed electron redistribution in the vicinity of the boundary plane.
The propensity for such redistributions is reflected in materials parameters such as electronegativities, polarisabilities and the differences between the values of the two sides of the interface. Strong adhesion is indirectly also related to the lattice matching or mismatch, because that influences the density of suitable in-teraction sites in the boundary plane.
Finally, fixed local charges, which are characteristic for ionic compounds, introduce additional Coulomb and image charge interactions. The present comparison aims at assessing those latter interactions by comparing material combinations with one ionic partner to completely non-ionic combinations.

Keywords: interfaces; density-functional; metal-ceramic; ferroic; semiconductor

  • Invited lecture (Conferences)
    CECAM-Workshop on Metal-Ceramic Interfaces, 20.-22.07.2009, Zürich, Schweiz

Permalink: https://www.hzdr.de/publications/Publ-13188
Publ.-Id: 13188


Multi-scale approaches for structure and conductivity of complex materials

Gemming, S.

In nanostructured materials spatial confinement effects lead to structure-dependent modifications of the bulk transport properties. In part, such modifications can be accounted for by a classical master equation approach for the transport of the different charge carrier species. The rather large quantity of parameters, which enter such an approach, can more or less easily be adjusted to the dimensional characteristics and the electronic settings of the system as well as to temperature effects. On the other hand, a microscopically more detailed and mostly parameter-free picture is obtained from a quantum-mechanical treatment on the basis of the density-functional theory. An extension by a Green's function formalism allows the determination and analysis of electronic transport through contacted nanostructures. Examples will be given to demonstrate the applicability of the different approaches for dissipative and hopping transport through a regular array of nanostructures, for a mechanically triggered metal-insulator transition in nanowires, and for the enhanced conductivity at multiferroic domain walls.

Keywords: conduction; density-functional; multi-scale

  • Invited lecture (Conferences)
    Colloquium on Multi-Scale Modeling, 04.05.2009, Wien, Österreich

Permalink: https://www.hzdr.de/publications/Publ-13187
Publ.-Id: 13187


Transport through nanostructures

Gemming, S.

In nanostructured materials spatial confinement effects lead to structure-dependent modifications of the bulk transport properties. In part, such modifications can be accounted for by a classical master equation approach for the transport of the different charge carrier species. The rather large quantity of parameters, which enter such an approach, can more or less easily be adjusted to the dimensional characteristics and the electronic settings of the system as well as to temperature effects. On the other hand, a microscopically more detailed and mostly parameter-free picture is obtained from a quantum-mechanical treatment on the basis of the density-functional theory. An extension by a Green's function formalism allows the determination and analysis of electronic transport through contacted nanostructures. Examples will be given to demonstrate the applicability of the different approaches for dissipative and hopping transport through a regular array of nanostructures, for a mechanically triggered metal-insulator transition in nanowires, and for the enhanced conductivity at multiferroic domain walls.

Keywords: transport; conduction; conductivity; multi-scale; calculation; density-functional

  • Lecture (Conference)
    Sächsisches Landesseminar Theoretische Chemie, 26.02.2009, Leipzig, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13186
Publ.-Id: 13186


The role of homophase and heterophase interfaces on transport properties in structured material

Gemming, S.; Kunze, T.; Morawetz, K.; Pankoke, V.; Luschtinetz, R.; Seifert, G.

In structured or self-organized materials spatial confinement effects lead to structure- and interface-controlled modifications of the bulk transport properties. In part, such modifications can be accounted for by a classical master equation approach for the transport of the different charge carrier species. The rather large quantity of parameters, which enter such an approach, can more or less easily be adjusted to the dimensional characteristics, local potential changes at interfaces, and the electronic settings of the system as well as to temperature effects. On the other hand, a microscopically more detailed and mostly parameter-free picture is obtained from a quantum-mechanical treatment on the basis of the density-functional theory. An extension by a Green's function formalism allows the determination and analysis of electronic transport through contacted nanostructures. Examples will be given to demonstrate the applicability of the different approaches for dissipative and hopping transport through a regular array of nanostructures, for a mechanically triggered metal-insulator transition in nanowires, and for the enhanced conductivity at multiferroic domain walls.

Keywords: conduction; calculation; OFET; ferroic; FerroFET; ferrorganics

Permalink: https://www.hzdr.de/publications/Publ-13185
Publ.-Id: 13185


First-principles study of ferroelectric domain walls in multiferroic bismuth ferrite

Lubk, A.; Gemming, S.; Spaldin, N. A.

We present a first-principles density-functional study of the structural, electronic, and magnetic properties of the ferroelectric domain walls in multiferroic BiFeO3. We find that domain walls in which the rotations of the oxygen octahedra do not change their phase when the polarization reorients are the most favorable and of these, the 109° domain wall centered around the BiO plane has the lowest energy. The 109° and 180° walls have a significant change in the component of their polarization perpendicular to the wall; the corresponding step in the electrostatic potential is consistent with a recent report of electrical conductivity at the domain walls. Finally, we show that changes in the Fe-O-Fe bond angles at the domain walls cause changes in the canting of the Fe magnetic moments which can enhance the local magnetization at the domain walls.

Keywords: Bismuth ferrite; multiferroic; ferroic; domain wall; boundary; density-functional; calculation; conductivity

  • Physical Review B 80(2009), 104110
    DOI: 10.1103/PhysRevB.80.104110
  • Poster
    DPG Frühjahrstagung der Sektion Kondensierte Materie (SKM) 2010, 21.-26.03.2010, Regensburg, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13184
Publ.-Id: 13184


Effect of low nitrogen concentrations on the electronic properties of InAs1−xNx

Patanè, A.; Feu, W. H. M.; Makarovsky, O.; Drachenko, O.; Eaves, L.; Krier, A.; Zhuang, Q. D.; Helm, M.; Goiran, M.; Hill, G.

We report cyclotron resonance (CR), transverse magnetoresistance (MR), and Hall effect studies of a series of n-type InAs1−xNx epilayers grown on GaAs with x up to 1%. The well-resolved CR absorption lines, the classical linear MR, Shubnikov–de Haas magneto-oscillations, and negative MR revealed in our experiments provide a means of probing the effect of the N atoms on the electronic properties of this alloy system and reveal qualitative differences compared to the case of the wider gap III-N-V compounds, such as GaAs1−xNx. In GaAs1−xNx electron localization by N levels that are resonant with the extended band states of the host crystal act to degrade the electrical conductivity at small x (~0.1%). These phenomena are significantly weaker in InAs1−xNx due to the smaller energy gap and higher energy of the N levels relative to the conduction band minimum. In InAs1−xNx the electrical conductivity retains the characteristic features of transport through extended states, with electron coherence lengths (l~100 nm at 2 K) and electron mobilities (µ=6×103 cm2 V−1 s−1 at 300 K) that remain relatively large even at x=1%.

Keywords: InAsN; dilute nitride; magnetotransport; cyclotron resonance

Permalink: https://www.hzdr.de/publications/Publ-13183
Publ.-Id: 13183


U(VI) biosorption and biomineralization by Sulfolobus acidocaldarius

Reitz, T.; Merroun, M. L.; Li, B.; Foerstendorf, H.; Rossberg, A.; Steudtner, R.; Selenska-Pobell, S.

Microorganisms, along with the abiotic physicochemical factors, strongly influence migration of uranium in nature. In contrast to the well investigated interactions of bacteria with uranium, the influence of archaea on the natural behaviour of this radionuclide is still not well studied. In this work the interactions of the acidothermophilic archaeon Sulfolobus acidocaldarius DSM 639 with U(VI) at acidic conditions (pH 1.5, 3, 4.5 and 6) were investigated. These pH values are relevant for some heavy metal and uranium polluted environments where S. acidocaldarius is also distributed. After the contact with the archaeal cells, U(VI) was rapidly complexed, whereby the binding capacity was strongly influenced by the pH value and the biomass concentration. A combination of X-ray absorption spectroscopy, Fourier-transform infrared spectroscopy, and time-resolved laser-induced fluorescence spectroscopy revealed that at highly acidic conditions (pH 1.5 and 3) U(VI) is predominantly bound to organic phosphate groups. At pH 4.5 carboxylic groups are involved in the U(VI) complexation as well. However, at this pH part of the added U(VI) was precipitated in inorganic uranyl phosphate mineral phases. The latter were the most predominant uranium complexes found after the treatment of the cells with U(VI) for 48 hours at pH 6. Transmission electron microscopic analysis of the cells treated at pH 4.5 showed extracellular and intracellular U(VI) accumulates. The extracellular complexes represented mainly inorganic uranyl phosphate complexes, which were formed due to the liberation of orthophosphate by the cells. The formation of the intracellular uranyl phosphate deposits is attributed to uncontrolled uptake of U(VI) as a result of the increased cell permeability due to the stress of the non-optimal pH and uranium toxicity. Our results demonstrate that at moderate acidic conditions S. acidocaldarius immobilizes U(VI) via biosorption and biomineralization.

  • Lecture (Conference)
    8th Symposium on remediation in Jena - “Jenaer Sanierungskolloqium”, 28.-29.09.2009, Jena, Deutschland
  • Lecture (others)
    Internes Seminar (Angewandte Naturwissenschaft), 22.11.2009, Freiberg, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13182
Publ.-Id: 13182


The role of Ge-related oxygen-deficiency centers in controlling the blueviolet photo- and electroluminescence in Ge-rich SiO2 via Er doping

Kanjilal, A.; Tsushima, S.; Götz, C.; Rebohle, L.; Voelskow, M.; Skorupa, W.; Helm, M.

Using combined electroluminescence (EL) and photoluminescence (PL) studies we establish that the energy transfer process from the Er3+ to the Ge-related oxygen-deficiency centers (GeODCs) plays the key role in enhancing the 404 nm EL intensity in Ge-rich SiO2. Er doping induced structural modification does not appear to be relevant, which is deduced from the 404 nm PL quenching with increasing Er concentration, implying a gradual loss of GeODCs. In contrast to PL, the 404 nm EL intensity increases by 0.3% Er doping followed by a gradual decrease in intensity for higher Er concentrations, which is described in terms of a competition between the energy transfer process and the gradual segregation of Er due to the destruction of GeODCs with Er doping. This fact is further discussed in the light of ab initio molecular orbital calculations.

Keywords: Ge; Er; EL; PL

Permalink: https://www.hzdr.de/publications/Publ-13181
Publ.-Id: 13181


Implantation-assisted Co-doped CdS thin films: Structural, optical, and vibrational properties

Chandramohan, S.; Kanjilal, A.; Sarangi, S. N.; Majumder, S.; Sathyamoorthy, R.; Som, T.

This paper reports on structural, optical, vibrational, and morphological properties of cobalt-doped CdS thin films, prepared by 90 keV Co+ implantation at room temperature. In this work, we have used cobalt concentration in the range of 0.34–10.8 at. %. Cobalt doping does not lead to the formation of any secondary phase, either in the form of metallic clusters or impurity complexes. However, with increasing cobalt concentration a decrease in the optical band gap, from 2.39 to 2.26 eV, is observed. This reduction is addressed on the basis of band tailing due to the creation of localized energy states in association with Urbach energy calculations. In addition, implantation gives rise to grain growth and increase in the surface roughness. Size and shape fluctuations of individual CdS grains, at higher fluences, give rise to inhomogeneity in strain. The results are discussed in the light of ion-matter interaction in the keV regime.

Keywords: CdS; Co doping

Permalink: https://www.hzdr.de/publications/Publ-13180
Publ.-Id: 13180


Domain-wall pinning and depinning at magnetic soft spots in nanowires

Wintz, S.; Vogel, A.; Moser, J.; Bolte, M.; Strache, T.; Fritzsche, M.; Im, M.-Y.; Fischer, P.; Meier, G.; Fassbender, J.

The controlled motion of magnetic domain walls (DWs) in nanowires is one of the fundamental issues for the realization of new concepts of high-density and ultrafast non-volatile data-storage devices. Locally welldefined confining potentials, e.g., created by notches, act as pinning sites for individual DWs . A spin polarized current, driven through the nanowire, yields the possibility to manipulate the magnetic configuration due to a transfer of spin-angular momentum. For a reliable spin-torque induced domain-wall depinning, low threshold currents are required in order to reduce stochastic temperature effects, caused by Joule heating as well as to avoid damage to the nanowire.

Here we present a concept to create pinning sites for DWs in magnetic nanowires without geometric constrictions:
The local modification of magnetic properties by means of ion irradiation (magnetic soft spots). Implantation of chromium ions into Ni80Fe20 causes a reduction of the saturation magnetization (Ms) and changes the crystalline magnetic anisotropy. The application of electron beam lithography (EBL) or focused ion beam (FIB) on the other hand enables a spatial resolution below 50 nm for this kind of magnetic patterning process. Pinning of DWs in magnetic soft spots is expected to be preferred compared to the environment, as the locally reduced Ms causes a decrease of the exchange energy associated with the DW. In order to verify the suitability of our concept, we fabricate magnetic soft spots into Ni80Fe20 nanowires by means of 15 kV Cr ion irradiation through an EBL shadow mask and examine the pinning characteristics for DWs.

In conclusion, magnetic soft spots realized via implantation of chromium are suitable as pinning sites for domain walls, avoiding a local increase of the current density in the nanowire due to supplementary spatial constriction.

Keywords: Magnetism; Domain Wall; Nanowire; Pinning; Soft-Spots

  • Poster
    11th Joint MMM-Intermag Conference, 18.-22.01.2010, Washington D.C., USA

Permalink: https://www.hzdr.de/publications/Publ-13179
Publ.-Id: 13179


Laser Particle Acceleration for Radiotherapy: A first radiobiological characterization of laser accelerated electrons

Pawelke, J.; Beyreuther, E.; Enghardt, W.; Kaluza, M.; Karsch, L.; Laschinsky, L.; Leßmann, E.; Naumburger, D.; Nicolai, M.; Richter, C.; Sauerbrey, R.; Schlenvoigt, H.-P.; Baumann, M.

In recent years, the technology of laser-based particle acceleration has developed at such a rate that compact and potentially more cost-effective accelerators are promised for medical application, e.g. for high precision hadron radiotherapy. Necessary requirements are the supply of stable and reliable particle beams with reproducible properties, sufficient particle intensities and monoenergetic spectra. Additionally, a precise dose delivery in an appropriate time and the exposure of a desired irradiation field are needed. Beside these physical demands, the consequences on detection and dosimetry as well as the radiobiological effect on living cells have to be investigated for the ultra-short pulsed laser-based particle beams. As a first step, the laser accelerator facility at the Jena Titanium:Sapphire system was customized for in vitro cell irradiation experiments and the delivered electron beam was im-proved with regard to its spectrum, diameter, dose rate and dose homogeneity. Furthermore, a custom-designed beam and dose monitoring system was established that enables real-time monitoring of the irradiation experiments and a precise determination of the dose delivered to the cells. Moreover, stable and reproducible beam properties were achieved during the whole three month experiment campaign. Dose-effect-curves were obtained for four cell lines and two endpoints, generally displaying a lower biological effectiveness for short-pulsed laser-accelerated electrons relative to the continuous 200 kV X-ray reference irradiation. Possible reasons will be discussed.

  • Lecture (Conference)
    World Congress on Medical Physics and Biomedical Engineering 2009, 07.-12.09.2009, München, Deutschland
  • Contribution to proceedings
    World Congress on Medical Physics and Biomedical Engineering 2009, 07.-12.09.2009, München, Deutschland
    WC 2009, IFMBE Proceedings 25/III: Springer, 502-504

Permalink: https://www.hzdr.de/publications/Publ-13178
Publ.-Id: 13178


Laser particle accelerators for radiotherapy – first radiobiological in vitro cell characterisation

Naumburger, D.; Beyreuther, E.; Enghardt, W.; Kaluza, M.; Karsch, L.; Laschinsky, L.; Leßmann, E.; Nicolai, M.; Pawelke, J.; Richter, C.; Sauerbrey, R.; Schlenvoigt, H.-P.; Baumann, M.

The novel technology of particle acceleration based on high intensity laser systems promises radiotherapy accelerators of compact size and reasonable costs. Laser acceleration results in ultra-short pulsed particle beams (in the region of 100 fs) with very high pulse dose rate (more than 1012 Gy/min) and is used in single shot physics experiments so far. Before a conceivable clinical application such particle beams have to be characterized in terms of their radiobiological properties and dosimetric detection and must allow a stable and reliable dose delivery. First in vitro cell irradiations with laser accelerated electron beams were performed and dose-effect-curves were obtained for four cell lines and two endpoints. Experiments have been performed at the Jena Titanium:Sapphire 10 terawatt laser system JETI, accelerating electrons to energies of up to 20 MeV. Before cell irradiation, the JETI system was optimized, adjusting the electron energy and beam spot size and improving the dose rate and homogeneity. Cell irradiations with doses in the range of 0.3 to 10 Gy have been performed for two squamous cell carcinoma cell lines with different radiosensitivity (FaDu, SKX) and two normal tissue cell lines (mammary gland epithelial cells 184A1, human skin fibroblasts HSF2). Each sample was equipped with radiochromic films used for retrospective precise dose determination. A Roos ionization chamber and a Faraday Cup monitored the beam providing online dose information necessary for irradiation control. Following to the irradiation the cell survival fraction was determined using clonogenic survival assay. Furthermore DNA double strand breaks were analyzed by immunochemical detection of the colocalized γH2AX and 53BP1 proteins 24 h after irradiation. Reference irradiation with a conventional X-ray tube (200 kV) was performed in parallel with experiments at JETI.
Samples were irradiated over a period of 3 months with described doses in which a reasonably stable and reproducible beam could be achieved monitored by the reliable accurate dosimetry system. The dose-effect-curves obtained indicate a lower biological effectiveness for the ultra-short pulsed laser accelerated electron beams in comparison with continuous X-rays. Possible reasons could be the different energy spectra impacting on cells as well as the low mean and ultra-high pulse dose rate of the electron beam. The effects will be discussed based on further experimental results.
This work has been supported by the German Federal Ministry of Education and Research (BMBF), grant no. 03ZIK445.

  • Lecture (Conference)
    37th Annual Meeting of the European Radiation Research Society, 26.08.-29.09.2009, Prague, Tschechische Republik

Permalink: https://www.hzdr.de/publications/Publ-13177
Publ.-Id: 13177


Does the high pulse dose rate affect the biological efficiency of laser accelerated electrons?

Beyreuther, E.; Karsch, L.; Laschinsky, L.; Leßmann, E.; Naumburger, D.; Richter, C.; Pawelke, J.

In recent years, the technology of laser-based particle acceleration was rapidly developed promising compact and potentially more cost-effective accelerators for medical applications, especially for hadron therapy. Beside specific physical requirements, e.g. stability and reliability of the particle beam as well as sufficient particle intensities, these ultra-short pulsed particle beams have to be investigated with regard to their radiobiological characteristics.
As a first step, in vitro cell irradiation experiments were performed using laser accelerated electron beams generated at the Jena Titanium:Sapphire laser system (JETI). Two biological endpoints, the clonogenic survival and remaining DNA double-strand breaks, were analyzed revealing in general a lower biological effectiveness for laser accelerated electrons relative to the continuous 200 kV X-ray reference source. Possible reasons might be the low mean and ultra-high pulse dose rate as well as the different electron spectra delivered to the cells.
The influence of the ultra-high pulse dose rate was assessed using pulsed electrons produced by the electron accelerator ELBE (Electron Linac for beams with high Brilliance and low Emittance) at the Forschungszentrum Dresden-Rossendorf. Based on a superconducting linear accelerator ELBE provides monoenergetic electrons of 20 MeV with a micropulse repetition rate of 13 MHz, a variable time structure that allows for single pulse or continuous irradiations and pulse doses tuneable over more than six orders of magnitude. Consequently, the ELBE beam can be used to mimic laser accelerated ultra-short pulses or for a continuous electron beam generated in a conventional radiotherapy linac.
Both pulse regimes were applied in the present study in order to investigate the influence of the pulse dose rate on the biological effectiveness independent on electron spectra, irradiation setup and dosimetry approach. The biological endpoints assessed at the JETI experiments were also analysed in two normal human cell lines (fibroblast, epithelial). In parallel, the clonogenic survival and DNA double-strand breaks remaining 24 hours post irradiation were also determined at the 200 kV X-ray reference source. To sum up the preliminary results, no significant differences were found for the biological effectiveness of continuous and ultra-short pulsed ELBE electrons relative to 200 kV X-rays. Further results and possible explanations will be discussed.
This work has been supported by the German Federal Ministry of Education and Research (BMBF) under contract 03ZIK445.

  • Lecture (Conference)
    37th Annual Meeting of the European Radiation Research Society, 26.08.-29.09.2009, Prague, Tschechische Republik

Permalink: https://www.hzdr.de/publications/Publ-13176
Publ.-Id: 13176


Laser particle accelerators for radiotherapy: first in vitro cell experiments with laser accelerated electron beams

Laschinsky, L.; Beyreuther, E.; Enghardt, W.; Karsch, L.; Leßmann, E.; Naumburger, D.; Nicolai, M.; Pawelke, J.; Richter, C.; Sauerbrey, R.; Schlenvoigt, H.-P.; Baumann, M.

Objective
The novel technology of particle acceleration based on high intensity laser systems promises accelerators of compact size and reasonable costs and may significantly contribute to a widespread use of high precision hadron radiotherapy. Although some basic properties of laser acceleration are reasonably well known from theory, simulations and fundamental physical experiments, several further requests have to be fulfilled for its medical application such as supply of a stable and reliable particle beam with reproducible properties and precise delivery of dose in an appropriate irradiation time with required exposure of a desired irradiation field. Moreover, the ultra-short pulsed (in the region of 100 fs) particle beams with resulting high pulse dose-rate (more than 1012 Gy/min) have to be characterized with regard to there radiobiological properties. First in-vitro cell irradiations with laser accelerated electron beams were performed and dose-effect-curves were obtained for four cell lines and two endpoints.

Material and Methods
Experiments have been performed at the Jena Titanium:Sapphire 10 terawatt laser system JeTi. Laser pulses (80 fs duration, 2.5 Hz repetition rate) were focused into a helium gas jet, accelerating electrons to energies of up to few ten MeV. Before irradiation, the JeTi system was optimized for cell experiments: the electron spectrum was limited to a minimum energy of 3 MeV, the beam spot size was adjusted and the dose rate and homogeneity were improved. Cell irradiations with doses in the range of 0.3 to 10 Gy have been performed for two squamous cell carcinoma (FaDu, SKX) and two normal tissue (mammary gland epithelial cells 184A1, human skin fibroblasts HSF2) cell lines. Each sample was equipped with two Gafchromic EBT radiochromic films, one in front and one behind the cell monolayer, used for retrospective precise dose determination. A Roos ionization chamber and a Faraday Cup monitored the beam providing on-line dose information necessary for irradiation control.
Following to the irradiation the cell survival fraction was determined using clonogenic survival assay. In addition, DNA double strand breaks present in cell 24 h after irradiation were analyzed by immunochemical detection of co-localized gamma-H2AX and 53BP1 molecules. Reference irradiation with a conventional X-ray tube (200 kV) was performed in parallel with experiments at JeTi.

Results
Normally used for physical single-shot experiments, the JeTi was customized for a long-time cell irradiation. Samples were irradiated at 13 experiment days over a period of 10 weeks. A reasonably stable and reproducible beam was achieved. Reviewed as average out of all cell irradiations a mean dose per pulse of 2.4 mGy was obtained. Comparing all samples, a variation in beam intensity of up to 40 % within one day and up to 130 % within all days was observed, but was compensated during cell irradiations by means of the on-line dose monitoring system. Dose homogeneity was examined for all samples within the target area and the inhomogeneity obtained was less than 10 % for all days and all applied doses. Although still preliminary, the dose-effect-curves obtained show in general a lower biological effectiveness for the laser accelerated electron beams in comparison with conventional X-rays. Possible reasons will be discussed.

Conclusions
Further experiments are prepared at a 100 terawatt laser system, which will lead to enhanced energy and intensity of the electron beam but also provide laser accelerated proton beams for cell irradiation studies.

The work was supported by the BMBF, grant no. 03ZIK445

Keywords: radiotherapy

  • Lecture (Conference)
    Fourth International Conference on Translational Research and Pre-Clinical Strategies in Radiation Oncology, 11.-13.03.2009, Geneva, Switzerland
  • Abstract in refereed journal
    Radiotherapy and Oncology 90(2009)Suppl 3

Permalink: https://www.hzdr.de/publications/Publ-13175
Publ.-Id: 13175


Systematic in vitro cell experiments with laser accelerated electron beams

Laschinsky, L.; Beyreuther, E.; Enghardt, W.; Karsch, L.; Leßmann, E.; Kaluza, M.; Naumburger, D.; Nicolai, M.; Pawelke, J.; Richter, C.; Sauerbrey, R.; Schlenvoigt, H.-P.; Baumann, M.

Purpose: The novel technology of particle acceleration based on high intensity laser systems promises ion radiotherapy accelerators of compact size and reasonable costs. Laser acceleration results in ultra-short pulsed particle beams with very high pulse dose-rate and is used in single shot physics experiments so far. Such particle beams have to be characterized in terms of their radiobiological properties and dosimetric detection and must allow a stable and reliable dose delivery before a conceivable clinical application. In a first step, systematic in vitro cell irradiations with laser accelerated electron beams were performed and dose-effect-curves were obtained.

Material: Experiments have been performed at the Jena Titanium:Sapphire (JeTi) 10 terawatt laser system. Laser pulses (80 fs duration) were focused into a helium gas jet, accelerating electrons to energies of up to 20 MeV. Before cell irradiation, the JeTi system was optimized, adjusting the electron energy and beam spot size and improving the dose rate and homogeneity. Cell irradiations were realized for two squamous cell carcinoma (FaDu, SKX) and two normal tissue (184A1, HSF2) cell lines in a dose range from 0.3 Gy to 10 Gy. For irradiation control a Roos ionization chamber and a Faraday Cup monitored the beam providing on-line dose information. Additional Gafchromic EBT radiochromic films were used for retrospective exact dose determination at the cell site. Referring to irradiation the survival fraction was determined and furthermore DNA double strand breaks were analyzed by immunochemical detection of the co-localized γH2AX and 53BP1 molecules 24 h after irradiation. A conventional X-ray tube (200 kV) was used for reference irradiation.

Results: The JeTi laser accelerator was successfully customized for long-time irradiation of cell samples with prescribed doses. Samples were irradiated at 13 experiment days over a period of 3 months. A reasonably stable and reproducible beam was achieved. Dose homogeneity was examined for all samples inside the target area and the inhomogeneity obtained was less than 10 % for all days and all applied doses. The determined dose-effect-curves show in general a reduced biological effectiveness for the laser accelerated electron beams in comparison with conventional X-rays. The effect of the high pulse dose-rate among the possible reasons will be discussed.

Conclusion: Further experiments are prepared at a 100 terawatt laser system, which will provide laser accelerated proton beams for cell irradiation studies.

This work was supported by the BMBF, grant no. 03ZIK445

  • Lecture (Conference)
    10th BIENNIAL ESTRO CONFERENCE ON PHYSICS AND RADIATION TECHNOLOGY FOR CLINICAL RADIOTHERAPY, 30.08.-03.09.2009, Maastricht, Netherlands
  • Contribution to proceedings
    10th BIENNIAL ESTRO CONFERENCE ON PHYSICS AND RADIATION TECHNOLOGY FOR CLINICAL RADIOTHERAPY, 30.08.-03.09.2009, Maastricht, Netherlands
    Radiother. Oncol. 92 (Suppl. 1)(2009) S89

Permalink: https://www.hzdr.de/publications/Publ-13174
Publ.-Id: 13174


Mit laserbeschleunigten Teilchen gegen Tumore – erste in vitro Experimente an laserbeschleunigten Elektronentrahlen

Naumburger, D.; Beyreuther, E.; Enghardt, W.; Karsch, L.; Lessmann, E.; Messner, L.; Nicolai, M.; Pawelke, J.; Richter, C.; Sauerbrey, R.; Schlenvoigt, H.-P.; Baumann, M.

Mit der neuartigen Technologie der Laser-Beschleunigung von Ionen werden kürzere Teilchenpakete (einige 10 Femtosekunden) mit wesentlich geringerer Pulsfrequenz und damit einhergehend einer viel höheren Puls-Dosisleistung erzeugt. Ziel ist es, durch Einsatz dieser Technologie die bisherige Strahlentherapie zu verbessern.
In einem ersten Schritt bei der Ermittlung einer möglicherweise veränderten biologischen Wirksamkeit dieser neuen Strahlenqualität wurden in vitro Bestrahlungsexperimente von Tumor- und Normalgewebszellen mit laserbeschleunigten Elektronen durchgeführt. Für die Experimente wurde das 10-Terawatt-Lasersystem JETI in Jena genutzt. Voraussetzung für die Zellbestrahlung war die Anpassung des Lasersystems und der Aufbau eines geeigneten Bestrahlungsplatzes einschließlich eines Dosimetriesystems. Im Anschluss an die Bestrahlung wurde das klonogene Zellüberleben mittels Koloniebildungstests bestimmt. Ergänzend hierzu wurde als weiterer biologischer Endpunkt der Nachweis der mit der DNA-Reparatur assoziierten Proteine g-H2AX und p53BP1 gewählt. g-H2AX reguliert als Histon die Zugänglichkeit der DNA für Reparaturmechanismen und ist mitverantwortlich für die Arretierung der Zelle in einer Phase des Zellzyklus als zelluläre Antwort auf niedrige Strahlendosen. Zusammen mit p53BP1 bildet es unmittelbar nach der Bestrahlung diskrete Foci an DNA-Doppelstrangbrüchen. Das verglichen mit unbestrahlten Proben erhöhte Auftreten von g-H2AX/p53BP1 Foci 24 h nach Bestrahlung ist ein Maß für residuelle, Dosis vermittelte DNA-Doppelstrangbrüche. Der Nachweis erfolgte mit dem g-H2AX/p53BP1 Foci Assay. Die Dosis-Effekt Kurven für beide Endpunkte werden präsentiert und diskutiert.
Die Genauigkeit beider Assays soll künftig durch Teilautomatisierung (z.B. FACS) verbessert werden. Des Weiteren wurde mit der Vorbereitung von Zellbestrahlungsexperimenten mit laserbeschleunigten Protonenstrahlen begonnen.

  • Lecture (Conference)
    11. Jahrestagung der Gesellschaft für Biologische Strahlenforschung GBS Tübingen, 06.-08.10.2008, Tübingen, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13173
Publ.-Id: 13173


Realistic integration of sorption processes in transport programs for long-term safety analysis

Brendler, V.; Stockmann, M.; Noseck, U.; Püschel, A.

Safety assessment of radioactive waste repositories in salt rock formations considers the overlying sedimentary rock above the salt domes as important barrier. Sorption on mineral surfaces of the sediment can retard the transport of many contaminants, namely radionuclides, considerably. Previously, the retention of radionuclides has been described in respective computer programs by temporally constant distribution coefficients.
In the present study, an existing transport program r3t [1] is extended towards a more realistic description of the radionuclide migration under changing geochemical conditions. The methodology developed here is based on a description of the sorption of radionuclides as a function of important influence factors such as pH, pCO2, ionic strength, and the mineral phases being present. Applying surface complexation models, multidimensional matrices of “smart Kd”-values can be computed a-priori. The reactive transport model r3t then can call for each time-space point Kd values adapted for the correct geochemical conditions. The biggest challenge here was finding a fast and robust algorithm for search and averaging in multidimensional matrices with non-equidistant population (see e.g. [2]). First results are presented for a test case where respective site-specific geochemical conditions in the overlying rock have been evaluated, mainly consisting of tertiary and quaternary sands and clays [3].
References:
[1] Fein, E., Software Package r3t. Model for Transport and Retention in Porous Media. Final Report. Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) mbH, Report GRS-192, Braunschweig 2004.
[2] McNames, J.: A fast nearest neighbor algorithm based on a principal axis search tree. IEEE Trans. Pattern Analysis Machine Intell. 23 (2001), 964-976.
[3] Klinge, H., Köthe, A., Ludwig, R.-R., Zwirner, R., Geologie und Hydrogeologie des Deckgebirges über dem Salzstock Gorleben. Z. Angew. Geol. 2 (2002), 7-15.

  • Poster
    ICEM'09, 11.-16.10.2009, Liverpool, Great Britain

Permalink: https://www.hzdr.de/publications/Publ-13171
Publ.-Id: 13171


P0802 - Hochgeordnete Nanostruktur und Sensor und deren Verwendung

Pollmann, K.; Raff, J.; Fahmy, K.

Die vorliegende Erfindung betrifft eine hochgeordnete Nanostruktur und Sensor, in der bzw. dem organische Molekülgruppen, die spezifische Bindungseigenschaften für ein Zielmolekül haben, geordnet gebunden sind, und deren Verwendung. Anwendungsgebiet dafür finden sich in der Biotechnologie, Verfahrenstechnik, Umwelttechnik und Pharmazie, insbesondere bei der Herstellung von Biosensoren, in der biomedizinischen Analytik, bei der Beseitigung von Schadstoffen und Pathogenen, in der DNA-Analytik, für die Herstellung von Filtermaterialien, für Separationsverfahren, für Katalysatoren und in der medizinischen Therapie. Die Aufgabe der Erfin-dung ist es, eine Struktur zur Verfügung zu stellen, in der organische Molekülgruppen, insbesondere Molekülgruppen, die spezifische Bindungseigenschaften haben, geordnet gebunden sind, und dadurch die von den organischen Molekülgruppen gebundenen Substanzen in die Nähe funktioneller Bestandteile zu bringen. Dies wird gelöst durch eine Nanostruktur, die selbstorganisierende Prote-ine, an die Aptamere oder andere organische Molekülgruppen, die spezifische Bindungseigenschaften für ein Zielmolekül aufweisen, gebunden sind, und an die selbst-organisierenden Proteine gebundene anorganische Nanopartikel enthält.

  • Patent
    DE 2008014298 A1 - 24 09. 2009
  • Patent
    EP 2101 175 A1 - 16. 09. 2009
  • Patent
    EP 2101175 B1 - 16.09. 2012

Permalink: https://www.hzdr.de/publications/Publ-13170
Publ.-Id: 13170


ESR in low-dimensional quantum magnets

Zvyagin, S. A.

hat nicht vorgelegen

  • Invited lecture (Conferences)
    National High Magnetic Field Laboratory, Tallahassee, 15.09.2009, Tallahassee, USA

Permalink: https://www.hzdr.de/publications/Publ-13169
Publ.-Id: 13169


On the long way to laser particle therapy: Results of radiobiological experiments with laser accelerated electrons and future experiments with laser accelerated protons

Richter, C.; Beyreuther, E.; Enghardt, W.; Kaluza, M.; Karsch, L.; Laschinsky, L.; Leßmann, E.; Naumburger, D.; Nicolai, M.; Pawelke, J.; Sobiella, M.; Sauerbrey, R.; Schlenvoigt, H.-P.; Schürer, M.; Baumann, M.

Background: The novel technology of particle acceleration based on high intensity laser systems promises proton therapy accelerators of compact size and reasonable costs. Laser acceleration results in ultra-short pulsed (≈100 fs) particle beams with very high pulse dose-rate (in the order of 1012 Gy/min). These beams have to be characterized with regard to their radiobiological and dosimetric properties and must allow a stable and reliable dose delivery before a conceivable clinical application is possible. The results of the worldwide first systematic in vitro cell irradiation experiments with laser accelerated electrons will be presented. Moreover, the developed dosimetric requirements for cell irradiation experiments with laser accelerated protons of low energy will be presented.

Material and Methods: The experiments with laser accelerated electrons have been performed at the Jena Titanium:Sapphire (JeTi) 10 TW laser system. Laser pulses were focused into a helium gas jet, accelerating electrons to energies of up to 20 MeV. Cell irradiations were realized for two squamous cell carcinoma and two normal tissue cell lines in a dose range from 0.3 Gy to 10 Gy. For irradiation control an ionization chamber and a Faraday Cup provided online dose information. Additional Gafchromic EBT radiochromic films were used for retrospective exact dose determination at the cell site. Referring to irradiation the survival fraction was determined and furthermore DNA double strand breaks 24 h after irradiation were analyzed.
Moreover, an integrated dosimetry and cell irradiation device (IDCID) has been designed and optimized for laser accelerated proton beams of low energy. It integrates an online- and absolute dosimeter system in combination with an in vitro cell irradiation device. Furthermore, the different detectors and dosimeters of the IDCID have been tested and cross calibrated at the tandem accelerator of the Forschungszentrum Dresden-Rossendorf. For the application of radiochromic films within the IDCID, EBT films have been calibrated for different proton spectra at the eye irradiation facility of the Helmholtz Zentrum Berlin.

Results:
The determined dose-effect-curves for laser accelerated electrons show in general a reduced biological effectiveness in comparison with conventional X-rays. The effect of the high pulse dose-rate among the possible reasons will be discussed. Furthermore, calibration curves for EBT films have been determined for 6 energies between 5 and 62 MeV. For energies between 10 and 62 MeV no significant energy dependence was found. Moreover, results of the optimization and cross calibration of the detectors included in the IDCID will be shown.

Conclusion: A laser particle accelerator was successfully used to perform long-time systematic in vitro cell irradiations. Further cell irradiation experiments with laser accelerated protons from a 100 TW laser system are prepared.

This work was supported by the BMBF, grant no. 03ZIK445

  • Poster
    PTCOG 48, 28.09.-03.10.2009, Heidelberg, Dresden

Permalink: https://www.hzdr.de/publications/Publ-13168
Publ.-Id: 13168


Energy dependence of EBT-1 radiochromic film response for photon (10 kVp - 15 MVp) and electron beams (6 - 18 MeV) readout by a flatbed scanner

Richter, C.; Karsch, L.; Woithe, J.; Pawelke, J.

Purpose: The aim of this paper is to investigate the energy dependence of the radiochromic film type, Gafchromic EBT-1, when scanned with a flatbed scanner for film readout.

Methods: Dose response curves were determined for 12 different beam qualities ranging from a 10 kVp x-ray beam to a 15 MVp x-ray beam and include also two high energy electron beam qualities (6 and 18 MeV). The dose responses measured as net optical density (netOD) for the different beam qualities were normalized to the response of a reference beam quality (6 MVp).

Results: A strong systematic energy dependence of the film response was found. The lower the effective beam energy the less sensitive the EBT-1 films get. The maximum decrease in dose for the same film response between the 25 kVp and 6 MVp beam qualities was 44 %. Additionally, a difference in energy dependence for different doses was discovered, meaning that higher doses show a smaller dependency on energy than lower doses. The maximum decrease in normalized netOD was found to be 25 % for a dose of 0.5 Gy relative to the normalized netOD for 10 Gy. Moreover, a scaling procedure is introduced, allowing the correction of the energy dependence for the investigated beam qualities and also for comparable x-ray beam qualities within the energy range studied.

Conclusions: A strong energy dependence for EBT-1 radiochromic films was found. The films were readout with a flatbed scanner. If the effective beam energy is known, the energy dependence can be corrected with the introduced scaling procedure. Further investigation of the influence of the spectral band of the readout device on energy dependence is needed to understand the reason for the different energy dependence found in this and previous works.

Keywords: flatbed scanner; radiochromic film; energy dependence; dosimetry

Permalink: https://www.hzdr.de/publications/Publ-13167
Publ.-Id: 13167


An integrated dosimetry and cell irradiation device for in vitro cell experiments withlaser accelerated protons

Richter, C.; Karsch, L.; Sobiella, M.; Weber, A.; Pawelke, J.; Baumann, M.

Background: The novel technology of particle acceleration based on high intensity laser systems promises accelerators of compact size and reasonable costs and may significantly contribute to a widespread use of hadron radiotherapy. Although some basic properties of laser acceleration are reasonably well known from theory, simulations and fundamental physical experiments, several requests have to be fulfilled for its medical application. Moreover, the ultra-short pulsed (≈100 fs) particle beams with resulting high pulse dose-rate (in the order of 1012 Gy/min) have to be characterized with regard to their radiobiological properties. Therefore a precise dosimetry is necessary that takes into account the special characteristics of the laser accelerated protons. Special attention has to be drawn on the low energy (<10 MeV) of the available laser accelerated proton beams.

Material and Methods: An integrated dosimetry and cell irradiation device has been designed and optimized for the use with a laser accelerated proton beam of low energy. The device consists of a kapton vacuum window, an ultra-thin (25 µm) ionisation chamber for online dose information, a faraday cup inset for absolute dosimetry that can be replaced with a cell holder inset for cell irradiations. Moreover radiochromic films, i.e. Gafchromic EBT, can be placed in the cell holder inset matching the plane of the cell mono layer. Radiochromic films can be used to determine the two dimensional dose distribution and also for absolute dosimetry. For these purposes Gafchromic EBT films have been calibrated for different proton spectra at the eye irradiation facility of the Helmholtz Zentrum Berlin. Moreover first tests of the Faraday cup and the ionisation chamber have been carried out at the tandem accelerator of the Forschungszentrum Dresden-Rossendorf to characterize these detectors.
Fig 1: Integrated dosimetry and cell irradiation device

Results: Calibration curves for EBT films have been determined for 6 energies between 5 and 62 MeV and doses between 0.5 and 15 Gy. For energies between 10 and 62 MeV no significant energy dependence was found, whereas for 5 MeV protons the film response is reduced by up to 25 % compared to the 62 MeV proton beam quality. Moreover, this reduction in film sensitivity is dose depend. At the tandem accelerator the dependency of the Faraday cup signal from air pressure and guard ring voltage was determined. A more detailed cross calibration of Faraday Cup, ionization chamber and radiochromic films is ongoing and will be presented.

Conclusion: An integrated dosimetry and cell irradiation device for in vivo cell irradiation experiments with laser accelerated protons of low energy was designed, built and started to characterize. This includes the calibration of radiochromic films (Gafchromic EBT) and first characterizations of the different detectors.

  • Poster
    440. Wilhelm and Else Heraeus Seminar - Lasergetriebene Teilchen- und Röntgen-Stahlung für die Medizin, 13.-17.09.2009, Frauenwörth, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13166
Publ.-Id: 13166


4D in-beam positron emission tomography for verification of motion-compensated ion beam therapy

Parodi, K.; Saito, N.; Chaudhri, N.; Richter, C.; Durante, M.; Enghardt, W.; Rietzel, E.; Bert, C.

Purpose: Clinically safe and effective treatment of intra-fractionally moving targets with scanned ion beams requires dedicated delivery techniques such as beam tracking. Apart from treatment delivery, also appropriate methods for validation of the actual tumor irradiation are highly desirable. In this contribution the feasibility of four-dimensionally (space and time) resolved, motion-compensated in-beam positron-emission-tomography (4DibPET) was addressed in experimental studies with scanned carbon ion beams.
Methods: A polymethyl methracrylate (PMMA) block sinusoidally moving left-right in beam's eye view was used as target, radiological depth changes were introduced by placing a stationary ramp-shaped absorber proximal of the moving target. Treatment delivery was compensated for motion by beam tracking. Time-resolved, motion-correlated in-beam PET data acquisition was performed during beam delivery with tracking the moving target, and prolonged after beam delivery first with the activated target still in motion and, finally, with the target at rest. Motion-compensated 4DibPET imaging was implemented and the results were compared to a stationary reference irradiation of the same treatment field. Data were used to determine feasibility of 4DibPET but also to evaluate offline in comparison to in-beam PET acquisition.
Results: 4D in-beam as well as offline PET imaging was found to be feasible and offers the possibility to verify the correct functioning of beam tracking. Motion-compensation of the imaged b+-activity distribution allows recovery of the volumetric extension of the delivered field for direct comparison with the reference stationary condition. Observed differences in terms of lateral field extension and penumbra in the direction of motion were typically less than 1 mm for both imaging strategies in comparison to the corresponding reference distributions. However, in-beam imaging retained a better spatial correlation of the measured activity with the delivered dose.
Conclusions: 4DibPET is a feasible and promising method to validate treatment delivery of scanned ion beams to moving targets. Further investigations will focus on more complex geometries and treatment planning studies with clinical data.

Keywords: in-beam PET; ion therapy; treatment verification; 4D; target motion

Permalink: https://www.hzdr.de/publications/Publ-13165
Publ.-Id: 13165


Nanostructuring of surfaces for biosensing and other "nano" applications

Günther, T.; Weinert, U.; Raff, J.; Pollmann, K.

Many bacteria are covered with a protein envelope. These surface layer (s-layer) proteins are closely attached and anchored to the secondary cell wall polymer. The proteins used in our group derive from strains of Lysinibacillus species isolated from a uranium mining waste pile near Johanngeorgenstadt, Saxony, Germany. Once purified the disassembled S-layer keep the ability of self-organizing and self-assembling on interfaces. In vitro they form a paracrystalline protein lattice with defined pores and cavities as it can be naturally found on the bacterial surface. These protein sheets either coil up to tube-like structures or attach to surfaces. In addition to the self- assembling and organizing properties these proteins can bind high amounts of heavy metals. The ability to form monomolecular layers at interfaces qualifies them as tool for nano-patterning of surfaces. We are able to cover various surfaces with these proteins with nearly full coverage. This is possible due to recrystallization of monomers on polyelectrolyte coated surfaces. The recrystallization process can be monitored by AFM. AFM-images show the periodic nature of the protein lattice. The monomolecular character of the attached protein lattice was proven during the growth and afterwards by nanolithographic removal of the proteins. Different functional groups of the proteins are provided as binding sites for modifications such as crosslinking of molecules or binding or nucleation of inorganic particles. Therefore the lattice is a perfect immobilization matrix for different compounds as well as the assembly of sensory surfaces. A recently started project aims the development of a sensor for the optical readout of a chemical signal.
The efficient metal binding combined with the periodic alignment is used in other applications to create nanoparticles with a narrow size distribution. Currently we are optimizing the composition of the particles for photocatalysis. The high metal binding capacity itself turns the proteins into a promising material for filtering solutions as it is naturally used by the bacteria.

Keywords: nanoparticles; S-layer; surface layer; biosensor; AFM; FRET; photocatalysis

  • Poster
    Natural and Biomimetic Mechanosensing, 26.-28.09.2009, Dresden, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13164
Publ.-Id: 13164


Retention of selenium oxyanions onto kaolinite and illite

Jordan, N.; Foerstendorf, H.; Brendler, V.

In the context of nuclear waste management, long-term safety assessments have shown that selenium-79, released from the solid waste matrix, could be one of the major isotopes contributing to the global radioactivity potentially reaching the biosphere. Selenium has a quite complex speciation, with four main oxidation states, depending on both the pH and the redox potential of the surrounding environment. Sorption onto minerals can strongly affect the availability and the mobility of selenium. It is thus of great importance to be able to characterize both at a macroscopic and a microscopic level the different processes (retention, reduction, surface precipitation, …) that can potentially take place.
Regarding the multi-barrier concept considered for deep underground storage of high level and long-lived radionuclides, clays are candidates as host rock as well as backfill materials. The main phases constituting clay rocks are minerals such as montmorillonite, bentonite, or illite, but also other compounds like iron oxides, titanium oxide, pyrite, calcite and organic matter. It has already been shown that clays and iron oxides can sorb and reduce selenium(VI) and selenium(IV) (Nguyen et al. (2005), Scheinost and Charlet (2008), Charlet et al. (2007)).
Thus, sorption experiments of selenium(VI) and selenium(IV) onto kaolinite and illite have been performed. Kaolinite and illite have been investigated since they are abundant and well crystallized clay mineral in soils. To get a better understanding of involved sorption mechanisms, a combination of both macroscopic and microscopic measurements have been used.
Kaolinite KGa1-b from the Clay Mineral Society repository has been used without further pretreatment. Illite du Puy (France) has been purified in order to remove auxiliary and minor phases to get a homo-ionic “Na-illite” clay. Then, batch experiments aiming at studying the sorption behaviour of selenium(IV) onto kaolinite and illite have been performed in NaCl and NaClO4. Preliminary results show that clays have higher affinity towards selenium(IV) compared to selenium(VI), which is an agreement with former studies on iron and aluminium oxides (Rovira et al. (2008). The influence of the suspensions´pH, as well as the ionic strength effect has been investigated. All the experiments have been performed under anoxic conditions in a glove box under N2 atmosphere (O2 < 1 ppm). Selenium speciation in solution has been checked using Hydride Generation-Atomic Absorption Spectroscopy measurements. The oxidation state of the selenium species once sorbed onto the kaolinite and illite surface has been evidenced using X-Ray Photoelectron Spectroscopy.
Electrophoresis measurements have also been performed during this work. Comparison between the zeta potential of the kaolinite and illite surfaces before and after selenium oxyanions retention has been done, to check whether the sorption takes place by chemical bonding formation or rather by electrostatic attraction.
Finally, ATR-FTIR measurements have been performed using an ATR ZnSe crystal. By comparison with former IR measurements concerning selenato and selenito-ligands containing complexes as well as phases with sorbed selenium species, the fashion binding of selenium(VI) and selenium(IV) onto illite has been evidenced.

  • Contribution to proceedings
    Clays in Natural and Engineered Barriers for Radioactive Waste Confinement, 29.03.-01.04.2010, Nantes, France, 413-414

Permalink: https://www.hzdr.de/publications/Publ-13163
Publ.-Id: 13163


Experiments and numerical simulations of horizontal two phase flow regimes

Höhne, T.; Vallee, C.

Stratified two-phase flow regimes can occur in the main cooling lines of Pressurized Water Reactors, Chemical plants and Oil pipelines. A relevant problem occurring is the development of wavy stratified flows which can lead to slug generation. Because slug flow 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. The recent improvements of the multiphase flow modelling in the ANSYS CFX code make it now possible to simulate these mechanisms in detail. In order to validate existing and further developed multiphase flow models, high-resolution measurement data is needed in time and also in space. For the experimental investigation of co-current air/water flows, the HAWAC (Horizontal Air/Water Channel) was built. The channel allows in particular the study of air/water slug flow under atmospheric pressure. Parallel to the experiments, CFD calculations were carried out. The two-fluid model was applied with a special turbulence damping procedure at the free surface. An Algebraic Interfacial Area Density (AIAD) model on the basis of the implemented mixture model was introduced, which allows the detection of the morphological form of the two phase flow and the corresponding switching via a blending function of each correlation from one object pair to another. As a result this model can distinguish between bubbles, droplets and the free surface using the local liquid phase volume fraction value. The behaviour of slug generation and propagation at the experimental setup was qualitatively reproduced by the simulation, while local deviations require a continuation of the work. The creation of small instabilities due to pressure surge or an increase of interfacial momentum should be analysed in the future. Furthermore, experiments with pressure and velocity measurements are planned and will allow quantitative comparisons, also at other superficial velocities.

Keywords: CFD; horizontal flow; Multiphase flow; HAWAC

  • Contribution to proceedings
    Seventh International Conference on CFD in the Minerals and Process Industries, 09.-12.12.2009, Melbourne, Australia
    CD-ROM
  • Invited lecture (Conferences)
    Seventh International Conference on CFD in the Minerals and Process Industries, 09.-12.12.2009, Melbourne, Australia

Permalink: https://www.hzdr.de/publications/Publ-13162
Publ.-Id: 13162


Validation of CFD codes and applications in NRS

Höhne, T.

Strong increase of usage of three-dimensional Computational Fluid Dynamics (CFD) in industrial applications because for instance
slugging,
pressurized thermal shocks,
coolant mixing,
thermal striping
cannot be predicted by traditional one-dimensional system codes with the required accuracy and spatial resolution.

Keywords: slugging; CFD; pressurized thermal shocks; coolant mixing

  • Invited lecture (Conferences)
    3rd Nordic Conference on Fluid Dynamics in the Power Industry, 15.-16.09.2009, Copenhagen, Danmark

Permalink: https://www.hzdr.de/publications/Publ-13161
Publ.-Id: 13161


On the formation of mixed vacancy-copper clusters in neutron-irradiated Fe-Cu alloys

Birkenheuer, U.; Ulbricht, A.; Bergner, F.; Gokhman, A.

To investigate the irradiation-induced degradation of the mechanical properties of Cu-containing reactor pressure vessel steels, a set of model alloys was fabricated and neutron-irradiated up to four different doses, 0.026, 0.052, 0.10, and 0.19 dpa, using the same neutron flux (140 x10-9 dpa/s). A series of complementary experimental techniques have been applied to these samples, including PAS and SANS. We report here the analyses the of small-angle neutron scattering (SANS) experiments for the two binary Fe-Cu model alloys: Fe-0.3%Cu and Fe-0.1%Cu. Size-resolved cluster distributions functions were extracted from the scattering data and characterized by the peak radius of the distribution and the total volume fraction of the detectable precipitate clusters. A significant difference in the results for the Cu-rich and the Cu-poor model alloys could be observed. The aim of the present study is to understand the observed trends on the base of rate theoretical (RT) cluster dynamic simulations.
To this end, the time evolution of the precipitate clusters under the given irradiation conditions were simulated using standard rate theory models for pure Cu clusters. While reasonable model parameters could be found to describe the experimental data of the Fe-0.3%Cu alloy, it was impossible to reproduce the data for the Cu-poor model alloy this way. By linking the rate theory models to classical nucleation theory it could be demonstrated that no RT model could do so – no matter how involved the point defect dynamics – as long as the Cu precipitation process itself is not changed. Different mechanisms can be thought off to result in such modifications, among them heterogeneous nucleation with nanovoids as nucleus for further Cu growth, or the formation of mixed vacancy-copper aggregates throughout.
We therefore augmented our rate theory model to allow for the additional absorption of vacancies by the Cu-rich precipitates and an accompanied change in the interface energy between iron matrix and mixed clusters. Adjusting the model parameters properly the entire set of data point for all four doses and both compositions could be reproduced giving confidence that the basic idea of our RT model are reasonable. In addition, it was possible to provide some estimates on the time evolution of the average composition of the precipitate clusters. They exhibit – without any re-fitting – the same trends as the experimental cluster compositions deduced from the A-ratio of the SANS signals.

Keywords: rate theory; Fe-Cu alloys; SANS

  • Poster
    XIV International Conference on Small-Angle Scattering, 13.-18.09.2009, Oxford, United Kingdom
  • Open Access Logo Journal of Physics: Conference Series 247(2010), 012011
    DOI: 10.1088/1742-6596/247/1/012011

Permalink: https://www.hzdr.de/publications/Publ-13160
Publ.-Id: 13160


SANS investigation of neutron-irradiated Fe-Cr alloys

Ulbricht, A.; Heintze, C.; Bergner, F.; Eckerlebe, H.

Ferritic-martensitic chromium steels are candidate materials for future applications in both Gen-IV fission and fusion technology. Experimental investigation of Fe-Cr alloys is important for the understanding of the effect of chromium on the irradiation behaviour of more complex alloys.
The materials investigated in this work are four binary Fe-Cr alloys of commercial purity with chromium contents between 2.5 and 12.5at%. Neutron irradiation was performed in the reactor BR2 at Mol (Belgium) at a temperature of 300°C and neutron flux of 9x1013 cm-2s-1 (E > 1 MeV). The neutron exposures expressed in units of displacements per atom correspond to 0.6 and 1.5 dpa.
In the SANS experiments carried out at the SANS-2 facility of GKSS, a wavelength of 0.58 nm and three detector-sample distances of 1, 4 and 16 m were used. The samples were placed in a saturation magnetic field. Special details related to the analysis of the SANS results (e.g. interference for concentrated solutions, bimodal distribution of scatterers) will be discussed in the full paper. The scattering curves obtained for the unirradiated conditions of the four Fe-Cr alloys were taken as reference in order to calculate difference scattering curves for the irradiated conditions.
We have found that (1) the volume fraction of scatterers slightly increases with neutron exposure (Fe-9at%Cr) or exhibits a saturation (Fe-2.5, 5 and 12.5at%Cr), (2) the volume fraction at 1.5 dpa is an increasing function of the chromium level with a slight increase up to Fe-9at%Cr and an abrupt increase between 9 and 12.5at%Cr, (3) the radii of irradiation-induced scatterers are essentially less than 8 nm and the size distributions can be reasonably described by a monomodal (Fe-2.5, 5 and 12.5at%Cr) or a bimodal (Fe-9at%Cr) distribution, (4) the A-ratio of 2.05 obtained for Fe-12.5at%Cr corresponds with the expectation for the alpha’-phase, (5) for the lower chromium levels the A-ratio can be explained neither as alpha’ nor as vacancy clusters alone, clusters composed of chromium and impurity carbon are possible candidates.
Conclusions will be drawn on the effect of the chromium content and the neutron exposure on the concentration and nature of the irradiation-induced scatterers. For the special case of Fe-12.5at%Cr the volume fraction of alpha’ and the solubility limit for chromium in iron at the irradiation temperature can be estimated.

Keywords: SANS; Fe-Cr alloys; neutron irradiation

  • Poster
    XIV International Conference on Small-Angle Scattering, 13.-18.09.2009, Oxford, United Kingdom
  • Open Access Logo Journal of Physics: Conference Series 247(2010), 012035
    DOI: doi:10.1088/1742-6596/247/1/012035

Permalink: https://www.hzdr.de/publications/Publ-13159
Publ.-Id: 13159


laser proton acceleration … aiming for cancer therapy

Schramm, U.

Invited talk at 440th WE Heraeus Seminar, Frauenwörth 2009, Laser driven particle and x-ray sources for medical applications

Keywords: laser proton acceleration; cancer ion therapy

  • Invited lecture (Conferences)
    Laser driven particle and x-ray sources for medical applications, 13.-17.09.2009, Kloster Frauenwörth, Chiemsee, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13158
Publ.-Id: 13158


Laser-accelerated ion beams for future medical applications

Kraft, S.

Recent success in laser-driven particle acceleration has increased interest in laser-generated “accelerator-quality” beams, for example, protons and ions have been produced with up to several tens of MeV per nucleon, and with extremely low emittance (<0.01 mm mrad, normalized). Compact, high-gradient laser-accelerators are therefore now being discussed as a potentially viable technology for a host of particle-beam applications, including future compact medical accelerators for medical diagnostics and therapy. After commissioning of a 150 TW laser system at the FZD, a joint research center for radiation therapy with laser-accelerator ions is being established together with the OncoRay Center for Radiation Research in Oncology, and the University Clinic of the Technical University of Dresden. The present status and future plans of the center, and the results from first proton acceleration experiments at FZD will be presented.

  • Lecture (Conference)
    World Congress on Medical Physics and Biomedical Engineering, 12.09.2009, München, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13157
Publ.-Id: 13157


Selenium(IV) retention onto ilite

Jordan, N.; Foerstendorf, H.; Brendler, V.

In the context of nuclear waste management, long-term safety assessments have shown that selenium-79, released from the solid waste matrix, could be one of the major isotopes contributing to the global radioactivity potentially reaching the biosphere. Selenium has a quite complex speciation, with four main oxidation states, depending on both the pH and the redox potential of the surrounding environment. Sorption onto minerals can strongly affect the availability and the mobility of selenium. It is thus of great importance to be able to characterize both at a macroscopic and a microscopic level the different processes (retention, reduction, surface precipitation, …) that can potentially take place.
Regarding the multi-barrier concept considered for deep underground storage of high level and long-lived radionuclides, clays are candidates as host rock as well as backfill materials. Clays like illite, kaolinite, montmorillonite and bentonite constitute the main phases of clay rocks, together with other compounds like iron oxides, titanium oxide, pyrite, calcite and organic matter. We decided to focus our work on Illite since it is an abundant and well crystallized clay mineral in soils.
Thus, retention properties of illite towards selenium(IV) have been investigated during this study, using a combination of both macroscopic and microscopic measurements.
Illite du Puy (France) has been used as the sorbing phase. It has been purified in order to remove auxiliary and minor phases to get a homo-ionic “Na-illite” clay. Then, batch experiments aiming at studying the sorption behaviour of selenium(IV) onto illite have been performed in NaClO4. The influence of the suspensions´pH, as well as the ionic strength effect has been investigated. All the experiments have been performed under anoxic conditions in a glove box under N2 atmosphere (O2 < 1 ppm). Selenium speciation in solution has been checked using Hydride Generation-Atomic Absorption Spectroscopy measurements. The oxidation state of the selenium species once sorbed onto the illite surface has been evidenced using X-Ray Photoelectron Spectroscopy.
Electrophoresis measurements have also been performed during this work. Comparison between the zeta potential of the illite surfaces before and after selenium(IV) sorption has been done, to check whether the sorption takes place by chemical bonding formation or rather by electrostatic attraction.
Finally, ATR-FTIR measurements have been performed using an ATR ZnSe crystal. By comparison with former IR measurements concerning selenito-ligands containing complexes as well as phases with sorbed selenium species, the fashion binding of selenium(IV) onto illite has been evidenced.

  • Contribution to proceedings
    16th Radiochemical Conference, 18.-23.04.2010, Mariánské Lázne, Czech Republic, 0009-2770, s115

Permalink: https://www.hzdr.de/publications/Publ-13156
Publ.-Id: 13156


Uranium(VI) Diffusion in Opalinus Clay in the Absence and Presence of Humic Acid

Joseph, C.; Schmeide, K.; Sachs, S.; Bernhard, G.

As possible host rock and backfill material for a nuclear waste repository clay is discussed. The interaction of the clay with actinides, especially uranium (U), is the focus of our work. Batch sorption and diffusion experiments are performed in order to estimate the actinide migration in clay formations. Furthermore, the influence of humic acid (HA) on these processes is investigated. HA are ubiquitously found in natural environments. In a worst case scenario these polyelectrolytic macromolecules can be transported by aquifers through the clay formation, where they can interact with e.g. actinides of the nuclear waste. Natural clay contains also HA and fulvic acid like organic matter, which can be released from the clay. The extraction of small organic ligands from natural clay was shown in literature (Courdouan et al. 2007). HA has a multitude of functional groups, which are able to complex metal ions, like U(VI), very well. HA also forms stable colloids. Due to this behavior HA can influence the mobility of U(VI) in a nuclear waste repository.
Currently, we are studying the diffusion of U(VI) in opalinus clay (Mont Terri, Switzerland) in the absence and presence of HA by diffusion experiments using synthetic opalinus clay pore water (Pearson 1998; pH 7.6, I = 0.39 M) as mobile phase. In our studies the assembly of Van Loon et al. (2004) is used, where an intact opalinus clay bore core (diameter: 2.57 cm, thickness: 1 cm) is put into a diffusion cell, which is connected with a high and a low concentration reservoir containing the mobile phase with the tracer. All experiments are performed under anaerobic conditions. The direction of diffusion is perpendicular to bedding. The pressure exerted on the bore core samples is 5 MPa. The density of the bore core pieces is 1.85 g/cm3. For the experiments two diffusion cells are used for investigation of i) U(VI) diffusion in the absence and ii) presence of HA. At first the diffusion properties of the opalinus clay samples in the diffusion cells were determined by through- and out-diffusion experiments using HTO as tracer. As diffusion parameters for HTO in opalinus clay De = (5.31 ± 1.01) x 10-11 m2/s and De = (7.23 ± 1.36) x 10-11 m2/s were determined. The diffusion accessible porosities of HTO were ε = 0.44 ± 0.08 and ε = 0.55 ± 0.10. These two different results for two bore core parts show the heterogeneity of the clay. However, the data are in agreement with literature data (e.g. Tevissen et al. 2004). For the U(VI) diffusion experiments 233U and 14C-labeled synthetic HA (Sachs et al. 2004) are used as tracer. The concentrations are set to [U] = 1 x 10-6 M and [HA] = 10 mg/L in synthetic opalinus clay pore water as mobile phase. So far, the experiments are carried out for three months. During this time no activity of 233U was measured in the low concentration reservoirs. That points out the good retention behavior of opalinus clay towards U(VI). However, this result is in contrast to results of batch sorption experiments with opalinus clay powder. There, a low sorption affinity of U(VI) towards opalinus clay was determined in pore water, although a higher surface area was accessible for U(VI) (specific surface area (BET) = 41.6 m2/g). Opalinus clay contains a calcite fraction of 13 % (Nagra 2002). The leached out calcium ions determine the speciation of U(VI) in the pore water, because the neutral aquatic complex Ca2UO2(CO3)3 (Bernhard et al. 2001) is formed, which dominates the U(VI) speciation (99 %). This complex sorbs only weakly onto opalinus clay (0.05 ± 0.002 µg U/m2 clay). The good retention ability of opalinus clay during the diffusion experiments can be attributed to the lack of free length of paths for the present Ca2UO2(CO3)3(aq) in the intact bore core piece. In contrast to the U(VI) diffusion, diffused HA molecules were measured in the low concentration reservoir 13 days after start of the experiment...

Keywords: uranium(VI); humic acid; opalinus clay; diffusion; pore water; particle size distribution

  • Contribution to proceedings
    Clays in Natural & Engineered Barriers for Radioactive Waste Confinement, 29.03.-01.04.2010, Nantes, France
    Uranium(VI) Diffusion in Opalinus Clay in the Absence and Presence of Humic Acid
  • Poster
    Clays in Natural & Engineered Barriers for Radioactive Waste Confinement, 29.03.-01.04.2010, Nantes, France

Permalink: https://www.hzdr.de/publications/Publ-13155
Publ.-Id: 13155


Selenite retention by nanocrystalline magnetite: Role of adsorption, reduction and dissolution/co-precipitation processes

Missana, T. A.; Scheinost, U.; Granizo, A. C.; García-Gutiérrez, M.

We studied selenite (SeO32-) retention by magnetite (FeIIFeIII2O4) using both surface complexation modeling and X-ray absorption spectroscopy (XAS) to characterize the processes of adsorption, reduction, and dissolution/co-precipitation.
The experimental sorption results for magnetite were compared to those of goethite (FeIIIOOH) under similar conditions. Selenite sorption was investigated under both oxic and anoxic conditions and as a function of pH, ionic strength, solid-to-liquid ratio and Se concentration. Sorption onto both oxides was independent of ionic strength and decreased as pH increased, as expected for anion sorption; however, the shape of the sorption edges was different. The goethite sorption data could be modeled assuming the formation of an inner-sphere complex with iron oxide surface sites (SOH). In contrast, the magnetite sorption data at low pH could be modeled only when the dissolution of magnetite, the formation of aqueous iron–selenite species, and the subsequent surface complexation of these species were implemented. The precipitation of ferric selenite was the predominant retention process at higher selenite concentrations (>1 104 M) and pH < 5, which was in agreement with the XAS results. Sorption behavior onto magnetite was similar under oxic and anoxic conditions. Under anoxic conditions, we did not observe the reduction of selenite. Possible reasons for the absence of reduction are discussed. In conclusion, we show that under acidic reaction conditions, selenite retention by magnetite is largely influenced by dissolution and co-precipitation processes.

Keywords: selenite; selenate; selenium; redox; sorption; EXAFS; structure; magnetite

Permalink: https://www.hzdr.de/publications/Publ-13154
Publ.-Id: 13154


Fano interference in the intersubband THz response of photoexcited GaAs/AlGaAs quantum wells

Wagner, M.; Golde, D.; Stehr, D.; Schneider, H.; Helm, M.; Andrews, A. M.; Roch, T.; Strasser, G.; Kira, M.; Koch, S. W.

In our work, we directly observe the interplay between ponderomotive contribution and true intersubband transition (IST). To this end, we probe the conduction IST of an undoped GaAs/Al0.34Ga0.66As multiple quantum well by transmitting broadband THz pulses after resonant photoexcitation with either a broad-band or narrowband laser at the 1s heavy-hole exciton. The field oscillations of the transmitted THz pulses are directly detected by phase-matched electro-optic sampling. We observe that the differential THz transmission transient as the pump-induced change in the transmitted THz field shows a strong beating. In the frequency domain this results in an intersubband resonance with a broad additional peak at lower energy. The line shape of this intersubband resonance strongly resembles a Fano-resonance with an undershoot at the low-frequency side and an asymmetric peak to higher frequencies. However, since we are able to measure differential transmission and total THz absorption separately, we find that the absorption does not show such a Fano-asymmetry, but reveals the expected Lorentzian-like line shape of the intersubband resonance. Especially, it is a single peak and therefore the beating in the time domain cannot originate from an adjacent second absorptive resonance next to the true IST resonance.
In our microscopic theory these features can be explained unambiguously by a phase-sensitive superposition of the true THz intersubband current and the ponderomotive current.

Keywords: Fano profile; THz probe; intersubband transition

  • Lecture (Conference)
    10th international conference on intersubband transitions in quantum wells ITQW2009, 06.-11.09.2009, Montreal, Canada

Permalink: https://www.hzdr.de/publications/Publ-13153
Publ.-Id: 13153


Experimental investigations on the condensation of steam bubbles injected into sub-cooled water

Lucas, D.; Beyer, M.; Szalinski, L.

Bubble condensation plays an important role e.g. in sub-cooled boiling or steam injection into pools. Since the condensation rate is proportional to the interfacial area density, bubble size distributions have to be considered in an adequate modelling of the condensation process. To develop and validate closure models for CFD codes new experimental data are required. The effect of bubble sizes is clearly shown in experimental investigations done at the TOPFLOW facility of FZD. Steam bubbles are injected into a sub-cooled upward pipe flow via orifices in the pipe wall located at different distances from measuring plane. 1 mm and 4 mm injection orifices are used to vary the initial bubble size distribution. The variation of the distance between the location of the gas injection and the measuring plane allows investigating the evolution of the flow along the pipe. Measurements are done using wire-mesh sensors and thermocouples. Condensation is clearly faster in case of the injection via the smaller orifices, i.e. in case of smaller bubble sizes. Data on averaged void fraction, radial gas volume fraction profiles, profiles of the gas velocity and bubble size distributions in dependency of the L/D ratio are presented in the paper.

Keywords: bubble flow; condensation; phase transfer; experiment; CFD

  • Contribution to proceedings
    5th European-Japanese Two-Phase Flow Group Meeting, 20.-25.09.2009, Spoleto, Italien
  • Lecture (Conference)
    5th European-Japanese Two-Phase Flow Group Meeting, 20.-25.09.2009, Spoleto, Italien

Permalink: https://www.hzdr.de/publications/Publ-13152
Publ.-Id: 13152


Complexation of aqueous uranium(IV) with phosphate investigated using time-resolved laser-induced fluorescence spectroscopy (TRLFS)

Lehmann, S.; Geipel, G.; Grambole, G.; Bernhard, G.

Heavy metals like the actinides possess a high risk potential to the environment not only because of their radiotoxicity but also due to their chemical toxicology. Uranium as one of the major actinide elements has to be considered in particular. Under reducing conditions, tetravalent uranium occurs primarily in the environment. To date, a lack of appropriate analytical techniques that featured sufficient sensitivity made it difficult to study the aqueous phosphate chemistry of uranium(IV) as such complexes show only low solubility. A novel time-resolved laser fluorescence spectroscopy system was set up recently and optimized to do research on uranium(IV). By application of this laser system we could successfully study uranium(IV) phosphate in concentration ranges where no precipitation or formation of colloids occurred. At pH = 1.0, U4+ and one uranium(IV) phosphate complex existed in parallel in aqueous solution. The complex could be identified as [U(H2PO4)]3+. Determination of its corresponding complex formation constant via two different evaluation methods resulted in the finding of (1) logß = 26.37 ± 0.76 and (2) logß = 26.43 ± 0.23. Both values are in very good agreement with each other and prove that [U(H2PO4)]3+ is a very stable complex in solution under experimental conditions.

Keywords: uranium(IV); phosphate; fluorescence spectroscopy; TRLFS; complex formation constant

  • Journal of Radioanalytical and Nuclear Chemistry 283(2010), 395-401

Permalink: https://www.hzdr.de/publications/Publ-13151
Publ.-Id: 13151


AER working group D on VVER safety analysis – report of the 2009 meeting

Kliem, S.

The AER Working Group D on VVER reactor safety analysis held its 18th meeting in Řež, Czech Republic, during the period 18-19 May, 2009. The meeting was hosted by the Nuclear Research Institute Řež. Altogether 17 participants attended the meeting of the working group D, 16 from AER member organizations and 1 guest from a non-member organization. The co-ordinator of the working group, Mr. S. Kliem, served as chairman of the meeting.

The meeting started with a general information exchange about the recent activities in the participating organizations.

The given presentations and the discussions can be attributed to the following topics:

• Code validation and benchmarking
• Safety analysis and code developments
• Reactor pressure vessel thermal hydraulics
• Future activities including discussion on the participation in the OECD/NEA Benchmark for Kalinin-3 VVER-1000 NPP

A list of the participants and a list of the handouts distributed at the meeting are attached to the report. The corresponding PDF-files can be obtained from the chairman.

  • Lecture (Conference)
    19th Symposium of AER on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, Varna, Bulgarien
  • Contribution to proceedings
    19th Symposium of AER on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, Varna, Bulgarien
    Proceedings of the 19th Symposium of AER on VVER Reactor Physics and Reactor Safety, Budapest: KFKI AEKI, 9789633726402, 523-529

Permalink: https://www.hzdr.de/publications/Publ-13150
Publ.-Id: 13150


Technology Platform from Nature: Bacterial S-Layers

Kutschke, S.; Matys, S.; Pollmann, K.; Raff, J.

Starting point of our research were radio-ecological investigations on the interaction of actinides with bacteria, recovered from uranium mining waste piles. Thereby several isolates were subsequently analyzed regarding their growth in presence of different heavy metals and their heavy metal binding properties, particularly using uranium. Some isolates show a high and selective binding for uranium, cadmium, lead, and a few other heavy metals. Interestingly, the heavy metals were immobilized on the cell surface, preventing any sustainable damage of the cell. Responsible for the binding of heavy metals outside the cell is a proteinaceous cell envelope, a so-called surface layer (S-layer). The highly ordered S-layers are often composed of identical protein monomers, that possess the ability to self-assemble into two-dimensional paracrystalline lattices. The highly regular structure of the S-layers with many pores of identical size and many regularly arranged functional groups offers good binding sites for different kinds of ions and molecules. Furthermore, the pores serve as nucleation sites for the formation of metal nanoclusters or minerals.
In consequence of the mentioned properties, detailed studies on the metal binding of bacterial S-layers were accomplished. As turned out, specific S-layers are able to bind uranium, arsenic, platinum and palladium. By immobilization of the S-layers, metal selective filter materials were developed. Furthermore, the regular structure of the S-layers can be utilized for the production of clustered metal and metal oxide nanoparticles for many different (photo)catalytic approaches, e.g. CNT synthesis, degradation of pharmaceuticals and detoxification of heavy metals. Pd, ZnO, and TiO2 nanoparticles immobilized on S-layer and/or S-layer coated industrial carriers were thusly produced and show a high catalytic activity in comparison to equally chemically produced nanoparticles. Moreover S-layers are very prospective for the development of compound specific biosensors by combining organic or inorganic fluorescence dyes with specific binding molecules.

Keywords: S-layer; biosensors; photocatalysis; metal removal; nanoparticles; catalyst; CNT syntesis

  • Lecture (Conference)
    WITS 2009 - Water, Innovation, Technology & Sustainability Conference, 23.-24.11.2009, Manaus, Brasilien
  • Contribution to proceedings
    WITS 2009 - Water, Innovation, Technology & Sustainability Conference, 23.-24.11.2009, Manaus, Brasilien

Permalink: https://www.hzdr.de/publications/Publ-13149
Publ.-Id: 13149


Schnelle Ionen für Europa - Das SPIRIT-Projekt

Möller, W.; Kolitsch, A.; Merchel, S.; Zier, M.; Spirit-Team

Das von der EU finanzierte SPIRIT-Projekt (Support of Public and Industrial Research using Ion beam Technology) [1] erlaubt Nutzern aus Forschung und Industrie den kostenfreien transnationalen Zugang zu Ionenstrahl-Infrastrukturen. Daneben fördert es die Weiterentwicklung der ionenstrahlbasierten Methoden und Instrumente zur Materialanalyse und –modifikation sowie die weitere Verbreitung der Verfahren in Gebieten aktueller Forschung und Technik. Die SPRIT-Partner sind die elf führenden Ionenstrahleinrichtungen in Europa.
Schnelle Ionen im Energie-bereich von ca. 10 keV bis 100 MeV werden von den SPIRIT-Partnern eingesetzt und externen Nutzern zur Verfügung gestellt. Diese Ionen dienen insbesondere der Modifikation und Analyse von Oberflächen, Grenzflächen, dünner Schichten und nanostrukturierten Systemen. Anwender aus der Grundlagenforschung und der angewandten Forschung nutzen diese schnellen Ionen in der Materialforschung, Lebens-, Geo- und Umweltwissenschaften, bis hin zur Analyse von Kunst- und Kulturgütern. So können z.B. Elementkonzentrationen zerstörungs- und standardfrei mittels Ionenstrahlanalysemethoden wie
• Rutherford-Rückstreu-Spektrometrie (Rutherford Backscattering Spectrometry - RBS)
• Kernreaktionsanalyse (Nuclear Reaction Analysis - NRA)
• Elastische Rückstreuanalyse (Elastic Recoil Detection - ERD)
• Teilchen-induzierte Röntgen- und Gamma-Emission (Particle-Induced X-Ray – PIXE und Gamma-Emission - PIGE).
bestimmt werden. Alle Elemente sind dabei zugänglich; die meisten Elemente in lateraler, manche sogar in 3-D-Auflösung mit einem analysierbaren Tiefenbereich von nm/µm und einer Tiefenauflösung von 0.5-30 nm. Typische Nachweisgrenzen sind 10 µg/g (H), 500 µg/g - 1% (He-O), 1 µg/g (F) bzw. 10-100 µg/g (Na-U).
Sieben SPIRIT-Partner stehen für den transnationalen Zugang allen Nutzern der europäischen Union kostenfrei zur Verfügung. Anträge [2] für selbst durchgeführte Experimente oder Auftragsarbeiten werden von einem internationalen Expertengremium begutachtet. Bei positiver Entscheidung werden alle Kosten inkl. der Reise- und Aufenthaltskosten von SPIRIT übernommen.

Referenzen
[1] www.spirit-ion.eu, 7.RP #227012. [2] http://www.spirit-ion.eu/application.html.

Keywords: ion beam analysis; ion beam modification

  • Poster
    Deutsche Tagung für Forschung mit Synchrotronstrahlung, Neutronen und Ionenstrahlen an Großgeräten (SNI2010), 24.-26.02.2010, Berlin, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13148
Publ.-Id: 13148


Bestimmung langlebiger Radionuklide mittels Beschleunigermassenspektrometrie (AMS) mit DREAMS

Merchel, S.; Kolitsch, A.; Akhmadaliev, S.; Möller, W.

Das Forschungszentrum Dresden-Rossendorf (FZD) erweitert sein Portfolio um eine weitere hochsensitive analytische Methode: die Beschleunigermassenspektrometrie (accelerator mass spectrometry = AMS). Diese Analysetechnik ist prädestiniert zur Bestimmung langlebiger Radionuklide, die entgegen der allgemein üblichen Zerfallszählung, nicht durch den eigentlichen Zerfall detektiert werden. Vielmehr werden die noch nicht zerfallenen Nuklide wesentlich effizienter massenspektrometrisch bestimmt. Dabei besitzt die AMS gegenüber der konventionellen Massenspektrometrie den Vorteil, dass sie Störsignale von Molekülionen oder Ionen ähnlicher Masse (Isobaren) effektiver unterdrücken kann. Die AMS liefert somit weitaus niedrigere Nachweisgrenzen (20000 Atome/g bzw. 10-9Bq) als die konventionellen Methoden.
Im Gegensatz zu den in Europa gängigen niederenergetischen AMS-Anlagen, die sich weitgehend auf die Bestimmung von 14C spezialisiert haben, wird die AMS-Anlage des FZD - DREAMS (DREsden AMS) - als erste moderne Anlage in der EU mit einer Terminalspannung von 6 MV betrieben werden. Anstelle eines üblichen van-de-Graaff-Prinzips zur Hochspannungserzeugung, garantiert ein Hochfrequenz-Kaskadengenerator höchste Stabilität. So wird DREAMS nicht nur hochempfindliche, sondern auch hochpräzise Messungen liefern.
Aufgrund der instrumentellen Weiterentwicklungen der AMS, die die Bestimmung von Isotopenverhältnissen im Bereich von 10-16 ermöglichen [1], haben sich die interdisziplinären Applikationsgebiete stark ausgeweitet. Anfänglich bevorzugt untersuchte Proben aus Kosmochemie, Astrophysik und nukleare Daten, werden zunehmend von Proben aus Strahlenschutz, Nuklearsicherheit, Nuklearentsorgung, Radioökologie, Phytologie, Ernährungswissenschaften, Toxikologie und Pharmakologie verdrängt. Die Inbetriebnahme von DREAMS in 2009, wird die interne Vernetzung der FZD-Forschungsaktivitäten in der Materialforschung, Strahlenphysik, Radiochemie und Radiopharmazie vorantreiben. Zudem wird DREAMS auch externen Nutzern zur Verfügung stehen. Die Bestimmung langlebiger Radionuklide wie 10Be, 26Al und 36Cl hat insbesondere in den Geo- und Umweltwissenschaften an Bedeutung gewonnen [2]. Durch deren Quantifizierung können prähistorische Ereignisse wie Vulkanausbrüche, Bergstürze, Tsunamis, Meteoriteneinschläge, Erdbeben und Gletscherbewegungen datiert werden. Untersuchungen an Eisbohrkernen erlauben zudem die Rekonstruktion und Vorrausage von Klimaveränderungen.

Referenzen [1] S. Merchel et al, Nucl. Instr. and Meth. B 266 (2008) 4921. [2] J.C. Gosse und F.M. Phillips, Quat. Sci. Rev. 20(2001) 1475.

Keywords: accelerator mass spectrometry; cosmogenic nuclides

  • Poster
    Deutsche Tagung für Forschung mit Synchrotronstrahlung, Neutronen und Ionenstrahlen an Großgeräten (SNI2010), 24.-26.02.2010, Berlin, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13147
Publ.-Id: 13147


Uranium(VI) accumulation in selected bacterial and fungal cells

Günther, A.; Merroun, M. L.; Geissler, A.; Selenska-Pobell, S.; Raff, J.

Bacteria and fungi in soil, sediment and water may have a significant influence on the transport of radionuclides and other heavy metals in nature. In addition to chemical and physical factors, that affect the migration behaviour of uranium, metabolic processes play an important role in its mobilisation or immobilisation. The aim of this project is to look for possible uranium uptake systems in selected bacteria and fungi, showing high uranium accumulation capacities. In our institute we are using different microscopic, spectroscopic and chromatographic methods for the localization of accumulated uranium and for the identification of binding relevant compounds on the cell surface and inside the cell.
The Arthrobacter strain JG37-Iso2, isolated from a soil sample of a uranium mining waste pile near the town of Johanngeorgenstadt (JG) in Germany, is able to accumulate large amounts of uranium inside the cell. Therefore systematic investigations of the growth behaviour, uranium binding and uranium accumulation of Arthrobacter JG37-Iso2 were performed. As indicated by the TEM analysis, uranium diffuses in the cells during the stationary growth phase, possibly due to a higher permeability caused by damages of the cell membranes. For comparison we also investigate the interaction of uranium(VI) with the reference strains Arthrobacter oxygen and Arthrobacter nicotinae. Both strains show a different binding behaviour for uranium. First spectroscopic results indicate the coordination of uranium via carboxylic groups of the cell compartments, whereas a additional co-ordination to organic phosphate groups can currently not be excluded.

  • Lecture (Conference)
    8th Symposium on remediation in Jena “Jenaer Sanierungskolloqium”: Geo-bio-processes at geochemical barriers Geo-bio-processes at geochemical barriers, 28.-29.09.2009, Jena, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13146
Publ.-Id: 13146


Burning plutonium and minimizing the radioactive waste in existing PWR

Mittag, S.; Kliem, S.

Long-lived radioactive actinides are produced in light water reactors (LWR) using conventional fuel. “Innovative” fuel matrices may reduce the breeding of these nuclides. However, inherent LWR safety features have to be preserved, which restricts the possibilities for new fuel-carrying matrices. Respective fuel-assembly and LWR-core safety studies indicate practicable new fuel options for the near future.

  • Lecture (Conference)
    19th AER SYMPOSIUM on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, St. St. Constantine and Elena resort (Varna), Bulgaria
  • Contribution to proceedings
    19th AER SYMPOSIUM on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, St. St. Constantine and Elena resort (Varna), Bulgaria, 363-370

Permalink: https://www.hzdr.de/publications/Publ-13145
Publ.-Id: 13145


Heterologous expression of the S-layer-like protein SllB induces the formation of long filaments of E. coli consisting of protein stabilized outer membrane

Lederer, F.; Günther, T.; Flemming, K.; Raff, J.; Fahmy, K.; Springer, A.; Pollmann, K.

Escherichia coli is one of the best studied microorganisms and is the mostly used host for genetic engineering. The gram-negative single cells are rod-shaped and filaments are usually not found. Here we describe the reproducible formation of elongated E. coli cells. During heterologous expression of the silent S-layer protein gene sllB from Lysinibacillus sphaericus JG-A12 in E. coli Bl21 (DE3) the cells are arranged as long cell chains and surrounded by a highly stable sheath with a length of >100 µm (defined as filaments) while growing at room temperature. In stationary growth phase, microscopic analyses show the formation of unusual long transparent tube-like structures enclosing separated single cells. The tube-like structures were isolated and analyzed by SDS-PAGE, IR-spectroscopy and different microscopic methods in order to identify their special composition and structure. We show that the tube-like structures are outer membrane-like, enriched in protein content and associated with the recombinant S-layer protein, indicating a disordered cell division. However, bacterial cells show a high viability and stability. To our knowledge, this is the first report of such drastic morphological changes of E. coli, induced by the expression of a foreign protein.

Keywords: S-layer; Outer membrane; morphology; tube; cell division

Permalink: https://www.hzdr.de/publications/Publ-13144
Publ.-Id: 13144


Investigation on accident management measures for VVER-1000 Reactors

Tusheva, P.; Schaefer, F.; Reinke, N.; Rohde, U.

A consequence of a total loss of AC power supply (station blackout) leading to unavailability of major active safety systems which could not perform their safety functions is that the safety criteria ensuring a secure operation of the nuclear power plant would be violated and a consequent core heat-up with possible core degradation would occur.


Currently a study which examines the thermal-hydraulic behaviour of the system is being performed. This paper focuses on the possibilities for delay or mitigation of the accident sequence to progress into a severe one by applying accident management measures. The strategy “Primary circuit depressurization” as a basic strategy, which is realized in the management of severe accidents is being investigated. By reducing the load over the vessel in severe accident conditions, prerequisites for keeping the state of the primary circuit are being created. The time-margins for operators’ intervention as key issues are being also assessed.


The analyses are performed applying the GRS (Gesellschaft für Anlagen- und Reaktorsicherheit mbH) thermal-hydraulic system code ATHLET. Comparative analysis of the accident progression for a station blackout event for a reference German PWR and a reference VVER-1000, taking into account the plant specifics is being investigated.

  • Contribution to proceedings
    19th AER SYMPOSIUM on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, St. St. Constantine and Elena resort, Bulgaria
    Investigation on accident management measures for VVER-1000 Reactors
  • Lecture (Conference)
    19th AER SYMPOSIUM on VVER Reactor Physics and Reactor Safety, 21.-25.09.2009, St. St. Constantine and Elena resort, Bulgaria

Permalink: https://www.hzdr.de/publications/Publ-13143
Publ.-Id: 13143


RPV material investigations of the former VVER-440 Greifswald NPP

Rindelhardt, U.; Viehrig, H.; Konheiser, J.; Schuhknecht, J.; Noack, K.; Gleisberg, B.

The real toughness response of RPV material can only be determined after the final shut down of the NPP. Such a chance is given now by investigating material from the former Greifswald NPP (VVER-440/230).
In the first part the paper deals with fast neutron fluence calculations and retrospective dosimetry based on Niobium. Unfortunately, a second neutron reaction besides Nb-93(n,n') leading to Nb-93m-activity is the reaction Mo-92(n,gamma)Mo-93. Based on the found Nb and Mo contents in the RPV material, it turned out that the Nb-93m generation on the Mo path mostly dominates over the fast neutron induced generation from Nb.
The comparison between the calculated and the measured Nb-93m activities typically resulted in deviations of 50%. Possible reasons for the observed differences are discussed.
In the second part first results of fracture mechanic investigations are reported. SE(B) specimens from three thickness positions were tested and evaluated according to the test standard ASTM E1921-05. Cleavage fracture toughness values, K-Jc. were determined and Master Curve based reference temperatures (T-0) were evaluated. The T-0 measured at the inner surface of the RPV did not represent the conservative condition. The T-0 of disc 1-1.3 located between the surface and 1/4 thickness is about 40K higher compared with those of the surface.
The measured K-Jc values are not enveloped by the 5% fractile indexed with T-0 according to the Master Curve concept. However, the 5% fractile indexed with the VERLIFE reference temperature RTTo that includes an additional margin envelops the measured K-Jc values. Therefore the VERLIFE lower bound curve conservatively describes the fracture toughness of the investigated weld metal.

  • Nuclear Engineering and Design 239(2009)9, 1581-1590

Permalink: https://www.hzdr.de/publications/Publ-13142
Publ.-Id: 13142


Corrosion Resistance of Aeronautics Alloys Treated by Plasma Immersion Ion Implantation (PIII)

Da Silva, G.; Ueda, M.; Otani, C.; Reuther, H.

To increase the corrosion resistance of Al7075-T7351 and Ti-6Al-4V alloys were performed treatments by PIII. Experiments were made by using a mixture of N2 and H2 at ratio of 1:1. The time of treatment varied between one and three hours to verify its influence on the electrochemical behavior of these materials. After implantation process the samples of the aluminum and titanium alloys showed improved corrosion resistance. The better result was obtained to Al7075 alloy, due its smaller corrosion current density presented at polarization tests.

  • Poster
    11th International Conference on Advanced Materials, 20.-25.09.2009, Rio de Janeiro, Brasil

Permalink: https://www.hzdr.de/publications/Publ-13141
Publ.-Id: 13141


Comparison of spectroscopic investigation and computer modelling of lanthanide(III) and actinide(III) speciation in human biological fluids

Barkleit, A.; Heller, A.; Baraniak, L.; Bernhard, G.

Radionuclides represent a serious health risk to humans in case of incorporation. To get a first insight into the transport and metabolism in the human organism, we compared the speciation of Eu(III) and Cm(III) in human biological fluids calculated by thermodynamic modelling with spectroscopic results obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS) with regard to the analogy of lanthanides and actinides.
For spectroscopic studies, fresh saliva and urine samples were collected from healthy volunteers and analyzed within few days. For TRLFS measurements, all samples have been spiked in vitro with europium or curium. To identify the dominant species the measured spectroscopic data were compared to reference spectra with single organic and inorganic constituents of the biological fluids.
The TRLFS spectra with urine showed that all samples with a pH below and all samples with a pH above 5.8 each exhibit strikingly similar spectra. The TRLFS spectra with saliva were all similar in the pH range between 5 and 8. Comparing the measured spectra with the reference data, we found that in urine at lower pH citrate complex species dominate the speciation of both metals while at higher pH and in saliva the spectra were identical to those in inorganic electrolyte solution.
The speciation calculation, carried out with the computer program MEDUSA and the accompanying hydrothermal database HYDRA, showed for urine in accordance to the experimental results at pH values around 5 a dominating citrate speciation for both metals. In contrast to the experiments resulted the calculation at higher pH values for urine and in the whole observed pH for saliva in a simple phosphate complexation. However, spectroscopic investigations signed of a more complex speciation behaviour which cannot be described with single inorganic complexes.
In conclusion, the comparison of experimental speciation investigation and computer modelling shows that because of their simplifications models cannot always image the complex natural processes correctly.

  • Contribution to proceedings
    Third European IRPA Congress, 14.-18.06.2010, Helsinki, Finland
    Third European IRPA Congress, Finland: STUK – Radiation and Nuclear Safety Authority, 978-952-478-551-8, 2318-2327
  • Poster
    Third European IRPA Congress, 14.-18.06.2010, Helsinki, Finland

Permalink: https://www.hzdr.de/publications/Publ-13140
Publ.-Id: 13140


Updated S-factors for the 7Be(p,gamma)8B reaction

Junghans, A. R.; Snover, K. A.; Mohrmann, E. C.; Adelberger, E. G.; Buchmann, L.

We present revised 7Be(p,gamma)8B S-factors based on our previously published measurements, using a more detailed target analysis and improved stopping powers.
Extrapolating our data below the 1+ resonance to solar energies using the latest cluster model calculations of Descouvemont, we find that S{17}(0) = 21.5 pm 0.6(expt) pm 0.6(theor) eV b. Fitting all modern, low-energy (p,$\gamma$) data with the same theory, we find a ``best" value S{17}(0) = 20.9 pm 0.6(expt) pm 0.6(theor) eV b.

Permalink: https://www.hzdr.de/publications/Publ-13139
Publ.-Id: 13139


Theoretical and numerical approaches to the forward problem and sensitivity calculation of a novel contactless inductive flow tomography

Yin, W.; Peyton, A.; Stefani, F.; Gerbeth, G.

A completely contactless flow measurement technique based on the principle of EM induction measurements—contactless inductive flow tomography (CIFT)—has been previously reported by a team based at Forschungszentrum Dresden-Rossendorf (FZD). This technique is suited to the measurement of velocity fields in high conductivity liquids, and the possible applications range from monitoring metal casting and silicon crystal growth in industry to gaining insights into the working of the geodynamo. The forward problem, i.e. calculating the induced magnetic field from a known velocity profile, can be described as a linear relationship when the magnetic Reynolds number is small. Previously, an integral equation method was used to formulate the forward problem; however, although the sensitivity matrices were calculated, they were not explicitly expressed and computation involved the solution of an ill-conditioned system of equations using a so-called deflation method. In this paper, we present the derivation of the sensitivity matrix directly from electromagnetic field theory and the results are expressed very concisely as the cross product of two field vectors. A numerical method based on a finite difference method has also been developed to verify the formulation. It is believed that this approach provides a simple yet fast route to the forward solution of CIFT. Furthermore, a method for sensor design selection based on eigenvalue analysis is presented.

Permalink: https://www.hzdr.de/publications/Publ-13138
Publ.-Id: 13138


Speciation of curium(III) and europium(III) in human urine samples

Heller, A.; Barkleit, A.; Bernhard, G.

Due to their radiation and heavy metal properties, radionuclides represent a serious health risk to humans in case of incorporation. To understand their toxicity, transport, deposition and elimination in the human organism, it is therefore crucial to elucidate their chemical behavior and properties on a molecular level. For trivalent actinides originating from nuclear power plants knowledge about their metabolism is very limited. In case of incorporation, they tend to accumulate in liver and skeleton and are excreted to maximum 10 – 20 % within the first week. Nevertheless this excretion occurs mainly through the kidneys, which are known to be particularly radiation sensitive.
To address the lack of knowledge, we studied the speciation of curium (as a representative of trivalent actinides) and europium (as the lanthanide analogue) in human urine and their complexation with single constituents. Since both of these heavy metals exhibit unique fluorescence properties, time-resolved laser-induced fluorescence spectroscopy (TRLFS) is an adequate tool for this purpose.
Fresh 24-hours-urine samples were collected from healthy volunteers and analyzed within few days. The inorganic composition of all samples was determined using mass spectrometry with inductive coupled plasma (ICP-MS) and ion chromatography (IC). Then all samples were spiked in vitro with curium or europium and single as well as time-resolved laser-induced fluorescence spectra were measured. We analyzed at least 10 different urine samples and were able to divide all samples into two different groups according to their fluorescence spectra.
We found that all samples with a pH below 5.6 and all samples with a pH above 6.0 each exhibit strikingly similar spectra. Compared to each other the spectra of both groups are very different and therefore easy to distinguish. Furthermore the lifetime of the metals in samples with higher pH is substantially longer than in samples with lower pH. ICP-MS and IC analysis revealed that the inorganic composition of samples which exhibit the same fluorescence spectra can vary broadly within magnitudes. Therefore the most important factor influencing the speciation of metals in human urine does not seem to be the composition but was determined to be the pH.
To identify the dominating species we also recorded the fluorescence spectra of both metals in electrolyte solution containing all inorganic but no organic components of urine. Furthermore we studied the complexation of both metals with urea and citric acid as main organic urine constituents. Comparing the measured spectra and lifetimes with this reference data, we found that at lower pH a complex citric acid species dominates the speciation of both metals while at higher pH the spectra where identical to those in electrolyte solution ruling out any involvement of organic ligands. The exact nature of this inorganic metal species has yet to be clarified.

Keywords: curium(III); europium(III); biofluids; speciation; TRLFS; trivalent actinides; human urine

  • Lecture (Conference)
    Radchem 2010 - 16th Radiochemical Conference, 18.-23.04.2010, Marianske Lazne, Czech Republic

Permalink: https://www.hzdr.de/publications/Publ-13137
Publ.-Id: 13137


Removal of As (V) from contaminated waters by microorganisms and isolated S-layers

Matys, S.; Stein, R.; Katzschner, B.; Raff, J.; Soltmann, U.; Böttcher, H.; Kießig, G.; Pompe, W.

With the objective to develop new filter materials for cleaning of arsenic contaminated waters based on sol-gel immobilized microorganisms various bacterial strains and their isolated surface layers were investigated. Interestingly, the binding capacity of four S-layers, namely that of Lysinibacillus sphaericus NCTC 9602, Bacillus soil isolates JG-B 53 and JG-B 62 as well as Geobacillus stearothermophilus ATCC 12980 was 1.5 to 5fold enhanced in comparison to the commercial sorbent Ferrosorp with As(V) model solutions. Thereby, a different binding behaviour between whole cells and their corresponding S-Layers could be observed even in dependence on the used arsenic concentration. AFM investigations revealed more elevated and expanded S-Layer agglomerates in the case of G. stearothermophilus ATCC 12980 after loading with As.

  • Poster
    8th Symposium on remediation in Jena “Jenaer Sanierungskolloqium”: Geo-bio-processes at geochemical barriers, 28.-29.09.2009, Jena, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13136
Publ.-Id: 13136


Antiproliferative effect of ferrocifen drug candidateson malignant pleural mesothelioma cell lines

Zanellato, I.; Heldt, J.-M.; Vessieres, A.; Jaouen, G.; Osella, D.

The purpose of this study was to investigate the antiproliferative potential of two novel bio-organometallic drug candidates, based on hydroxyl-phenyl-but-1-ene skeleton and containing the ferrocenyl (Fc) moiety, namely ferrociphenol (Fc-diOH) and ferrocifen (Fc-OH-TAM), on two cell lines, named BR95 (epithelial-like) and MM98 (sarcomatous-like), obtained from pleural effusions of previously untreated malignant pleural mesothelioma (MPM) patients. In vitro chemosensitivity of MPM cells towards the title compounds was evaluated by cell viability assay, alkaline Single Cell Gel Electrophoresis (Comet test) and western blotting evaluation of p53 induction. The two bio-organometallic derivatives were found to be more potent in inhibiting cell proliferation than the reference metallo-drug cisplatin (CDDP). This antiproliferative effect cannot be attributed to estrogenic/antiestrogenic activity, since both cell lines resulted to be estrogen insensitive (ER−). Fc-diOH and CDDP were able to upregulate wild type p53 present in MM98 cell line, while Fc-OH-TAM was not. Similarly, Fc-diOH and CDDP induced early DNA damage, while Fc-OH-TAM did not. This indicates that, albeit the similar structures, the two ferrocifens exhert different mechanisms of cytotoxicity on MPM cells.

Keywords: Malignant mesothelioma; Antiprloliferative activity; Ferrocifens; Bio-orgometallic chemistry

Permalink: https://www.hzdr.de/publications/Publ-13135
Publ.-Id: 13135


The French accelerator mass spectrometry facility ASTER: Improved performance and developments

Arnold, M.; Merchel, S.; Bourlès, D. L.; Braucher, R.; Benedetti, L.; Finkel, R. C.; Aumaître, G.; Gottdang, A.; Klein, M.

After the installation and acceptance test of the French 5 MV AMS facility ASTER, the focus has been on improving 10Be and 26Al routine measurements. Quality assurance was established by introducing traceable AMS standards for each nuclide, self-monitoring by taking part in round-robin exercises and proficiency testing, and surveillance of long- and short-time variability of blank and reference materials. A background level of 3x10-14 makes ASTER well-suited for measuring 41Ca/40Ca in the 10-12 region, which is sufficient for a wide range of applications. Routine AMS measurements of volatile elements like 36Cl and 129I are most likely feasible in the very near future after sophisticated ion source improvements took place.

Keywords: accelerator mass spectrometry; terrestrial cosmogenic nuclides (TCN); calibration

Permalink: https://www.hzdr.de/publications/Publ-13133
Publ.-Id: 13133


Visualization of microorganisms in acidophilic biofilms

Brockmann, S.; Arnold, T.

Biofilms are ubiquitous and so they can also be found in regions with high concentrations of heavy metals. Due to their ability to change geochemical parameters e.g. O2-concentrations, Eh, pH, and by generating metabolites they are very important for the investigation of transport processes of heavy metals in nature. However, the influence of biofilms on the migration of uranium in contaminated environments, e.g. the former uranium mining areas in eastern Germany, was disregarded so far. In the former underground uranium mine in Königstein thick biofilms in form of streamers were observed in the mine adit drainages and in form of dripstone-like biofilms with slimy endings.
The biofilm structure was visualized by confocal laser scanning microscopy (CLSM). Fluorescent dyes were used for staining the microorganisms and the extracellular polymeric substances (EPS). Unfortunately, the biofilms from acid mine drainages (AMD) have pH-values not higher than 3 and the most common fluorescent dyes are not stable below pH-values of 4. Hence, the first step in this study was to find new acid-stable fluorescent dyes to stain the acidophilic microorganisms without any increase of the pH. For this purpose a variety of new fluorescent dyes were tested and the most suitable ones were compared with the common fluorescent dyes DAPI and SYTO 59. It was found that the selected new fluorescent dyes did very well stain acidophilic biofilm microorganisms whereas DAPI and SYTO 59 fail.

  • Poster
    8th Symposium on remediation in Jena “Jenaer Sanierungskolloquium”: Geo-bio-processes at geochemical barriers, 28.-29.09.2009, Jena, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13132
Publ.-Id: 13132


TRLFS investigation on seepage waters of the Gessenbach grassland

Baumann, N.; Arnold, T.

Laser fluorescence techniques possess some superior features, above all a very high sensitivity for fluorescent heavy metal ions. The predominance of TRLFS compared to other spectroscopic techniques, e.g. XRD and IR was showed in Baumann N. et al. (2008) in analyzing the speciation of U(VI) in a thin layer of an alteration product formed on depleted uranium. With their high sensitivity TRLFS is also suited to identify the U(VI) speciation in plant constituents. Long delay steps in time-resolved measurements avoid annoying fluorescence emission caused by organic substances.
Uranium speciation in seepage water of the Gessenbach grassland was determined by TRLFS. This was done to compare it in a later stage with the uranium speciation in plants, which grow on that grassland and ingest the same uranium contaminated water during their growth. The uranium content in those samples GB 3 and GB 6 was 75.1 and 291 ppb, respectively, and both samples delivered an evaluable fluorescence signal for TRLFS. The positions of the six peak maxima from these signals are in both water samples in concordance with data for uranium sulfate species published in the literature, e. g. in Bernhard G. et al. (1996) at 477, 493, 513, 537, 562 and 591 nm. Moreover, the time-resolved fluorescence signals of both water samples possess a mono-exponential decay, indicating the presence of one species only. These two characteristics, i.e. positions of peak maxima and lifetimes revealed without doubt that the uranium speciation in the seepage water is dominated by uranium (VI) sulfate species.
TRLFS measurements with plant compartments (e.g. roots, leaves, shoots) which grow in association with the seepage water will be carried out in future investigations. U(VI) components could be extracted from the plant compartments by centrifugation as cell sap, or as solid milled plant compartment sample and subsequently studied by TRLFS. Information in preparation of the plant compartments for TRLFS analyses has been reported in Günther A. et al. (2003) and were further refined. As suggested by Carrière M. et al. (2005) reactivity and toxicity of uranium depend on the speciation of heavy metals and accordingly have to be considered as important possible risk factor as uranium may enter economic plants and eventually arrives in the food chain.

Baumann N. et al. Environ. Sci. Technol. 42 8266-8269 (2008)
Bernhard G. et al. Radiochim. Acta 74 87-91(1996)
Günther A. et al. Radiochim. Acta 91 319-328 (2003)
Carrière M. et al. Nucl. Instrum. Methods Phys. Res. Sect. B-Beam Interact. Mater. Atoms 231, 268-273 (2005)

  • Lecture (Conference)
    8th Symposium on remediation in Jena “Jenaer Sanierungskolloquium”: Geo-bio-processes at geochemical barriers, 28.-29.09.2009, Jena, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13131
Publ.-Id: 13131


On the coupled solution of a combined population balance model using the least-squares spectral element method

Zhu, Z.; Dorao, C. A.; Lucas, D.; Jakobsen, H. A.

In this work, a cross-sectional averaged two-fluid model combined with a population balance model is applied to simulate the flow field and the bubble size distributions in a two-phase bubble column. The Martinez-Bazan breakage kernel and a modified Prince and Blanch coalescence kernel have been chosen to describe bubble breakage and bubble coalescence, respectively. In the present study, we discuss the use of a higherorder spectral element methodsthe least-squares methodsto compute the system of equations in a coupled manner. The least-squares method is highly accurate and has a number of advantages over the conventional numerical methods like the finite difference and finite volume methods. In contrast to the finite volume method, when desinging an overall solution algorithm, this least-squares method ensures that all the continuity equations are satisfied individually and it deals with both the convective and diffusive terms stably and accurately. The novel iterative algorithm solves the flow and the population balance equation in a coupled manner. The model has been validated against experimental data obtained for two-phase flow in a bubble column. The predicted bubble size distribution and other flow quantities are in good agreement with the experimental data.

Keywords: population balance; bubble; coalescence; breakup

  • Industrial & Engineering Chemistry Research 48(2009), 7994-8006

Permalink: https://www.hzdr.de/publications/Publ-13130
Publ.-Id: 13130


Uranium speciation in biofilms studied by Laser fluorescence techniques

Arnold, T.; Großmann, K.; Baumann, N.

Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behavior. The mechanisms of these processes are currently not understood. This is due to the complexity occurring in such biofilms creating many discrete geochemical microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical parameters, e.g. pH and dissolved oxygen concentration, their presence of organic molecules, e.g. metabolites, and many more. All of them may affect the metal speciation. To obtain such information, which are necessary for performance assessments studies or the development of new cost effective strategies for cleaning waste waters, it is however very important to develop new non-invasive methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques possess some superior features above all a very high sensitivity for fluorescent heavy metals. An approach of combining confocal laser scanning microscopy and laser induced fluorescence spectroscopy to study the interactions of biofilms with uranium is presented and it was found that the coupling of these techniques is a promising tool to study in situ in non-invasive fashion fluorescent heavy metals within biofilm systems. Information on uranium speciation and uranium redox states can be generated.

Keywords: biofilm; uranium; confocal laser scanning microscopy (CLSM); laser-induced fluorescence spectroscopy (LIFS)

Permalink: https://www.hzdr.de/publications/Publ-13129
Publ.-Id: 13129


Characterization of single ZnO nanorods by conductive atomic force microscopy

Beinik, I.; Kratzer, M.; Wang, L.; Brauer, G.; Anwand, W.; Teichert, C.

  • Poster
    Joint Annual Meeting of the Austrian Physical Society (ÖPG), 02.-04.09.2009, Innsbruck, Austria

Permalink: https://www.hzdr.de/publications/Publ-13128
Publ.-Id: 13128


Characterisation of ZnO single crystals – a challenge to positron annihilation spectroscopy

Brauer, G.

  • Lecture (others)
    Seminar am Institut für Kristallzüchtung Berlin, 17.08.2009, Berlin, Germany
  • Lecture (others)
    Seminar an der Charles University Prague, 02.11.2009, Prague, Czech Republic

Permalink: https://www.hzdr.de/publications/Publ-13127
Publ.-Id: 13127


Pattern rotation in the anisotropic Kuramoto-Sivashinsky equation

Keller, A.; Nicoli, M.; Cuerno, R.; Facsko, S.; Möller, W.

The formation of regular nanopatterns during low energy ion sputtering of solid surfaces has become a topic of intense research. This research is mainly motivated by promising applications of nanopatterned surfaces e.g. in thin film growth. On the other hand, these surfaces represent an interesting example of spontaneous pattern formation in non-equilibrium systems exhibiting different features like wavelength coarsening or a transition to spatiotemporal chaos. Different pattern types are observed for different experimental conditions, i.e. wavelike ripple patterns and hexagonally ordered dot arrays under oblique and normal ion incidence, respectively [1].
According to the model of Bradley and Harper (BH) [2], the regular patterns result from the competition between curvature dependent roughening and diffusional smoothing of the surface. Since the local erosion rate is higher in troughs than on crests, the eroded surface is unstable against any periodic perturbances. In the presence of a smoothing mechanism, however, wave vector selection occurs and a periodic pattern with a characteristic spatial frequency is observed. During recent years, several nonlinear extensions of the linear BH model have been proposed with the stochastic Kuramoto-Sivashinsky (KS) equation having played a prominent role [3]. However, although most experimental investigations on ion-induced pattern formation were performed under oblique ion incidence, only few theoretical studies focused on the corresponding anisotropic KS (aKS) equation.
In this work, we have investigated the influence of anisotropy on the morphology evolution in numerical integrations of the aKS equation. For a strong nonlinear anisotropy, a rotation by 90° of the initially formed ripple pattern was observed for intermediate and long integration times. Comparison with analytical predictions indicates that the observed rotated ripple pattern arises from anisotropic renormalization properties of the aKS equation. This result may also offer an explanation for the recent observation of transient structures in high-temperature experiments on Si(111) [4].

[1] W. L. Chan and E. Chason, J. Appl. Phys. 101, 121301 (2007)
[2] R. Bradley and J. Harper, J. Vac. Sci. Technol. A 6, 2390 (1988)
[3] R. Cuerno and A.-L. Barabási, Phys. Rev. Lett. 74, 4746 (1995)
[4] A.-D. Brown, J. Erlebacher, W.-L. Chan, and E. Chason, Phys. Rev. Lett. 95, 056101 (2005)

  • Poster
    Workshop Nanoscale Modification of Surfaces and Thin Films, 30.08.-03.09.2009, Rathen, Germany

Permalink: https://www.hzdr.de/publications/Publ-13125
Publ.-Id: 13125


The use of Th in HTR: state of the art and implementation in Th/Pu fuel cycles

Mazzini, G.; Bomboni, E.; Cerullo, N.; Fridman, E.; Lomonaco, G.; Shwageraus, E.

Nowadays nuclear power is the only greenhouse-free source that can contribute appreciably to the solution of the increasing world-wide energy demand problem. The use of Thorium in the nuclear energy production may offer some unique advantages to accomplish this task. Extensive research and development on the thorium fuel cycle has been conducted in many countries around the world. Starting from the current nuclear waste policy as well as from the (V)HTR good capabilities of Pu burning, the EU PUMA project focus on core physics investigations, in order to further demonstrate the potential benefits of using the HTR core as a Pu/MA transmuter. In this paper the following aspects have been analyzed:
– The state of art about the studies focusing on the use of Th in different core concepts
– The use of Th in HTRs, with a particular emphasis on Th-Pu fuel cycles
– An original assessment of Th-Pu fuel cycles in HTR, on the basis, the energy produced totally, per initial Pu and the ratio between discharged and loaded Pu mass
Some aspects related to Thorium exploitation were outlined, with a particular emphasis on its suitability for working in pebble-bed HTR as a fertile element in a Th-Pu fuel cycle, that is a promising kind of fuel considered in the framework of the EU PUMA project. Particularly, the influence of the Th/Pu weight fraction at BOC in a typical HTR pebble was analyzed as far as the reactivity trend vs. burn-up, the energy produced per Pu unit mass, and the Pu isotopic composition at EOC are concerned. The obtained results suggest us that there is not a best composition for the PBMR Pu/Th fuel. However deeper investigations need to be performed in order to draw final conclusions. Thus, at the moment it is possible to state that some optimized Th percentage in the initial Pu/Th fuel could be suggested on the basis of the aim we are trying to reach.

  • Open Access Logo Science and Technology of Nuclear Installations 2009(2009), 749736

Downloads:

Permalink: https://www.hzdr.de/publications/Publ-13124
Publ.-Id: 13124


Preliminary evaluation of a nuclear scenario involving innovative gas cooled reactors

Vezzoni, B.; Cerullo, N.; Forasassi, G.; Fridman, E.; Lomonaco, G.; Romanello, V.; Shwageraus, E.

In order to guarantee a sustainable supply of future energy demand without compromising the environment integrity, some actions for a substantial reduction of CO2 emissions are nowadays deeply analyzed. One of them is the improvement of the nuclear energy use. In this framework, innovative gas-cooled reactors, both the thermal and the fast solutions, seem to be very attractive for the electricity production point of view and for the potential industrial use along the high temperature processes (e.g. H2 production by steam reforming or I-S process). This work focuses on a preliminary (and conservative) evaluation of possible advantages that a symbiotic cycle (EPR-PBMR-GCFR) could entail, with special regard to the reduction of the HLW inventory and the optimization of the exploitation of the fuel resources. The comparison between the symbiotic cycle chosen and the reference one (once-through scenario – EPR-SNF directly disposed) shows a reduction of the time needed to reach a fixed reference level from ~170000 years to ~1550 years, time comparable with typical human times and for this reason more acceptable by the public opinion. In addition, this cycle enable to have a more efficient use of resources involved, obtaining that the total electric energy produced becomes equal to 630.54 TWh/year (instead of only 529.62 TWh/year, case of only EPR) without consuming additional raw materials.

  • Open Access Logo Science and Technology of Nuclear Installations 2009(2009), 940286

Permalink: https://www.hzdr.de/publications/Publ-13123
Publ.-Id: 13123


Interactions of Sulfolobus acidocaldarius with uranium

Reitz, T.; Merroun, M. L.; Rossberg, A.; Selenska-Pobell, S.

Interactions of the acidothermophilic archaeon Sulfolobus acidocaldarius DSM 639 with U(VI) were studied by using a combination of wet chemistry, X-ray absorption spectroscopy (XAS), and time-resolved laser-induced fluorescence spectroscopy (TRLFS). We demonstrated that at pH 2 this archaeal strain possesses a low tolerance to U(VI) and that its growth is limited to a uranium concentration below 1.1 mM. At similarly high acidic conditions (pH 1.5 and 3.0), covering the physiological pH growth optimum of S. acidocaldarius, at which U(VI) is soluble and highly toxic, rapid accumulation of the radionuclide by the cells of the strain occurred. About half of the uranium bind-ing capacity was reached by the strain after an incubation of five minutes and nearly total saturation of the binding sites was achieved after 30 minutes. Both, EXAFS- and TRLF-spectroscopic analyses showed that the accumulated U(VI) was complexed mainly through organic phosphate groups. The EXAFS measurements revealed that U(VI) is coordinated to the organic phosphate ligands of the archaeal cells in a monodentate binding mode with an average U-P bond distance of 3.60 ± 0.02 Å.

Keywords: Uranium; Archaea; Tolerance; Biosorption; EXAFS; TRLFS

  • Radiochimica Acta 98(2010), 249-257

Permalink: https://www.hzdr.de/publications/Publ-13119
Publ.-Id: 13119


System Solution for In-Beam Positron Emission Tomography Monitoring of Radiation Therapy

Shakirin, G.

In-beam Positron Emission Tomography (PET) is a system for monitoring high precision radiation therapy which is in the most cases applied to the tumors near organs at risk. High quality and fast availability of in-beam PET images are, therefore, extremely important for successful verification of the dose delivery. Two main problems make an in-beam PET monitoring a challenging task. Firstly, in-beam PET measurements result in a very low counting statistics. Secondly, an integration of the PET scanner into the treatment facility requires significant reduction of the sensitive surface of the scanner and leads to a dual-head form resulting in imaging artifacts. The aim of this work is to bring the imaging process by means of in-beam PET to optimum quality and time scale. The following topics are under consideration:
- analysis of image quality for in-beam PET;
- image reconstruction;
- solutions for building, testing, and integration of a PET monitoring system into the dedicated treatment facility.

Keywords: in-beam PET; radiation therapy

  • Book (Editorship)
    Dresden: TUDPress, 2009
    112 Seiten
    ISBN: 978-3-941298-33-0

Permalink: https://www.hzdr.de/publications/Publ-13118
Publ.-Id: 13118


In-situ X-ray scattering investigations at ROBL

Baehtz, C.; Jeutter, N.; Grenzer, J.; von Borany, J.

The beamline BM20 operated by the Forschungszentrum Dresden-Rossendorf is located at ESRF storage ring and divided into two stations for spectroscopy and diffraction in the range of 6 to 30 keV. The core competences of material research station are different in-situ X-ray scattering and diffraction investigations also combined with X-ray spectroscopy using a dual magnetron sputtering deposition chamber. Hereby the syntheses of SiO2/GeOx multilayers to create Ge nanocrystalls with well defined sizes by thermal decomposition afterward or directly by sputtering at elevated temperature were investigated. These are promising materials is in the field of solar cells. On the other side by the use a hemispherical Beryllium dome (optional with electrical resitivity four-point setup) the catalyst formation for the carbon nano tubes synthesis was characterized by in-situ diffraction experiment under controlled reactive atmosphere. By in-situ investigations process were characterized on-line and structural und functional properties are correlated directly with each other, which increase the comprehension of synthesis and processing of functional materials.

Keywords: in-situ; diffraction; carbon nano tubes; magnetron sputtering

  • Poster
    Euromat 2009, 07.-10.09.2009, Glasgow, UK

Permalink: https://www.hzdr.de/publications/Publ-13117
Publ.-Id: 13117


Comparison of PET Concepts for Dose Delivery Monitoring of Particle Therapy

Kunath, D.; Braess, H.; Fiedler, F.; Laube, K.; Parodi, K.; Priegnitz, M.; Shakirin, G.; Enghardt, W.

Tumor therapy using particle beams is highly precise and requires methods for monitoring of dose delivery. Solutions based on positron emission tomography (PET) are successfully implemented for the radiation therapy with carbon ions and protons at the Gesellschaft für Schwerionenforschung, Darmstadt, Germany, at the Heavy Ion Medical Accelerator at Chiba, Japan, at the Massachusetts General Hospital, Boston, USA, at the Hyogo Ion Beam Medical Center, Japan as well as at the National Cancer Center Kashiwa, Japan. Furthermore, the PET monitoring technique has been tested experimentally for 3He, 7Li, and 16O. The main requirements for the PET monitoring are (1) to produce images containing relevant information for the evaluation of dose delivery and (2) to reduce the additional time required for imaging as much as possible. There are three technical realizations: (1) In-beam PET (measurement during the irradiation), (2) In-room PET (measurement immediately after the irradiation of each portal using a PET scanner placed in the therapy room), (3) Off-line PET (measurement after the complete irradiation by means of a PET scanner located in a different room). These three concepts have been evaluated concerning workflow, counting statistics, and imaging. The treatment workflow is mostly affected by off-line PET. In the case of in-room and off-line PET, the counting statistics is approximately one half of that for in-beam PET if reasonable measuring times (<= 15 min) are assumed. Furthermore, there is an information loss using off-line PET. Thus, in-beam and in-room PET are the most feasible concepts to integrate PET into the particle therapy for dose monitoring.

Keywords: Positron emission tomography; dose monitoring; particle therapy

  • Contribution to proceedings
    Medical Physics and Biomedical Engineering World Congress, 07.-12.09.2009, München, Deutschland, Berlin Heidelberg New York: Springer, 978-3-642-03897-6
  • Lecture (Conference)
    Medical Physics and Biomedical Engineering World Congress, 07.-12.09.2009, München, Deutschland

Permalink: https://www.hzdr.de/publications/Publ-13116
Publ.-Id: 13116


Simulation des Boreinspeisesystems und seiner Reaktivitätswirksamkeit in einem Siedewasserreaktor (SWR)

Laczkó, G.

Der vorliegende Bericht befasst sich mit der Modellierung des Vergiftungssystems TW und der Simulation von auslegungsüberschreitenden Störfalltransienten, in denen eine Boreinspeisung erfolgt. Die Modellierung des Vergiftungssystems beinhaltet die Simulation des Transports und der Reaktivitätswirksamkeit des Bors während einer beliebigen Transiente. Das Modell berücksichtigt den Verlust des Boranteils, der in die Dampfphase übergeht (Dampfflüchtigkeit des Bors) und damit im Hinblick auf den Neutronenhaushalt verloren geht. Um die Dampfflüchtigkeit des Bors quantitativ zu berücksichtigen, wurden die aktuellen Messdaten der TU Dresden herangezogen. Diese Arbeit wurde im Rahmen eines gemeinsamen Förderprogramms zwischen dem Forschungszentrum Dresden-Rossendorf (FZD) und der Vattenfall Europe Nuclear Energy (VENE) durchgeführt.

  • Article, self-published (no contribution to HZDR-Annual report)
    Forschungszentrum Rossendorf 2009
    FZD\FWS\2009\01
    112 Seiten
    ISSN: 1437-322X

Permalink: https://www.hzdr.de/publications/Publ-13115
Publ.-Id: 13115


Efficient THz sideband generation in GaAs/AlGaAs multi quantum wells

Wagner, M.; Schneider, H.; Winnerl, S.; Helm, M.; Roch, T.; Andrews, A. M.; Schartner, S.; Strasser, G.

We have investigated the third-order nonlinear mixing process between a near-infrared laser and a free-electron laser in an undoped symmetric GaAs/AlGaAs multi quantum well. AC THz electric fields which couple strongly with intraband excitations in semiconductors can lead to spectral sidebands of simultaneous interband excitation. In this nonlinear mixing process a near-infrared (NIR) laser beam is mixed with the THz beam to generate sidebands around the NIR frequency with a frequency spacing equal to the THz frequency or multiples of it: ω = ω_NIR ± n × ω_THz (with integer n). We have investigated the third-order nonlinear mixing process between a near-infrared laser and a free-electron laser (FEL) in an undoped symmetric GaAs/AlGaAs multi quantum well. The sample is studied in transmission under illumination by FELBE, the free-electron laser (FEL) of the Forschungszentrum Dresden-Rossendorf. We use the tunability of the FEL to study the dependence of the mixing efficiency on THz wavelength. We find resonances related to heavy- to light-hole transitions, but also to the heavy-hole intra-exciton 1s-2p transition. It turns out that the conversion efficiency of the n=+2 sideband is largest (up to 0.1 %) for the 1s-2p intra-exciton transition, which is comparable to values previously reported for n=+1.

Keywords: THz sidebands; nonlinear mixing; intraexcitonic transition

  • Poster
    EDISON16, 24.-28.08.2009, Montpellier, Frankreich

Permalink: https://www.hzdr.de/publications/Publ-13112
Publ.-Id: 13112


On the spectrum of the magnetohydrodynamic mean field α2-dynamo operator

Günther, U.; Langer, H.; Tretter, C.

The existence of magnetohydrodynamic mean-field α2-dynamos with spherically symmetric, isotropic helical turbulence function α is related to a non-self-adjoint spectral problem for a coupled system of two singular second oder ordinary differential equations. We establish global estimates for the eigenvalues of this system in terms of the profile α and its derivative α'. They allow us to formulate an anti-dynamo theorem and a non-oscillation theorem. The conditions of these theorems, which again involve α and α', must be violated in order to reach overcritical and oscillatory regimes, respectively.

Keywords: magnetohydrodynamics; MHD; alpha-dynamo; anti-dynamo theorem; oscillation; polarity reversal; field reversal; oscillating dynamo; operator theory; non-self-adjoint operator; resolvent estimates

Permalink: https://www.hzdr.de/publications/Publ-13111
Publ.-Id: 13111


Fano profile in the intersubband THz response of photoexcited GaAs/AlGaAs quantum wells

Wagner, M.; Golde, D.; Stehr, D.; Schneider, H.; Helm, M.; Andrews, A. M.; Roch, T.; Strasser, G.; Kira, M.; Koch, S. W.

In our work we probe the conduction intersubband transition of an undoped GaAs/Al0.34Ga0.66As multiple quantum well via broadband terahertz pulses after resonant photoexcitation at the 1s heavy-hole exciton. The pump-induced change in the transmitted terahertz field shows a strong beating. In the frequency domain this results in an asymmetric Fano-like line shape for the intersubband resonance and an additional broad low-frequency peak. However, the total THz absorption shows only the single symmetric peak of the intersubband transition. In our microscopic theory these signatures unambiguously originate from the phase sensitive superposition of ponderomotive and terahertz intersubband currents.

Keywords: Fano profile; THz probe; intersubband transition

  • Lecture (Conference)
    EDISON16, 24.-28.08.2009, Montpellier, Frankreich
  • Open Access Logo Journal of Physics: Conference Series 193(2009), 012073
    DOI: 10.1088/1742-6596/193/1/012073

Permalink: https://www.hzdr.de/publications/Publ-13110
Publ.-Id: 13110


Absorptions- und Emissionsspektroskopische Messungen an Chlorophyll und entsprechenden Derivaten

Jentsch, A.

Ziel dieser Arbeit ist es, die Wechselwirkung von Chlorophyll a mit Uranylionen zu untersuchen. Es wurde eine methanolische Chlorophylllösung mittels Absorptionsspektroskopie charakterisiert. Das Absorptionsmaxima befindet sich bei 665,1 nm. Anschließend wurde das Zentralatom aus dem Komplex entfernt. Das Absorptionsmaximum der erhaltenen Pheophytinlösung liegt bei 653,1 nm. Nach Zugabe von Uranylnitrat war eine bathochrome Verschiebung des Peakmaxima nach 691,3 nm zu beobachten. Die aufgenommenen Emissionsspektren deuten ebenfalls darauf hin, dass der Uranylchlorophyll-Komplex synthetisiert werden konnte. Bei ausreichendem Überschuss an Uranylionen wird das Magnesium im Chla-Molekül durch UO22+ ersetzt.
Anhand der Absorptionspektren wurde versucht, die Assoziationskonstante K für die Bildung des U-Chla-Komplexes aus Pheophytin a zu ermitteln. Man erhält log K = 4,70 ± 0,35.

Keywords: chlorophyll; pheophytin

  • Other report
    TU Dresden: Bachelorarbeit (Studiengang Chemie), 2009
    40 Seiten

Permalink: https://www.hzdr.de/publications/Publ-13109
Publ.-Id: 13109


Laser Cooling at ESR, CSR and FAIR

Bussmann, M.; Schramm, U.; Dimopoulou, C.; Kozhuharov, C.; Kuehl, T.; Noertershaeuser, W.; Steck, M.; Stoehlker, T.; Winters, D.; Ma, X.; Wen, W.; Zhang, D.; Geppert, C.; Novotny, C.; Birkl, G.; Walther, T.

Laser cooling of ion beams is a promising technique to achieve ultracold ion beams of unprecedented brilliance in storage rings. Recent experiments at the ESR/GSI have shown that laser cooling at relativistic beam energies is feasible, opening the route towards laser cooling at future storage rings such as SIS300/FAIR. In this talk we present recent results on laser cooling of C3+ ion beams at the ESR. The results presented show that with laser-cooling space-charge dominated ion beams are observed with at least one order of magnitude smaller momentum spread than attained with electron cooling. This allows to reach the regime of strong coupling, which is a prerequisite for beam crystallization. Based on these results we present new experiments planned at ESR and CSR which will take full advantage of all-optical beam diagnostics that will allow to overcome the limited resolution of standard ion beam diagnostics. In combination with all-optical cooling schemes which do not rely on initial electron cooling of the ion beam, laser cooling is one of the most promising candidates for cooling ion beams at ultra-relativistic energies accessible at the future FAIR facility.

Keywords: laser cooling; relativistic ion beam; esr; csr; fair; optical diagnostics; pulsed laser; schottky pickup; momentum spread; strongly coupled plasma; crystalline ion beam

  • Invited lecture (Conferences)
    International workshop on beam cooling and related topics, COOL'09, 31.08.-04.09.2009, Lanzhou, China

Permalink: https://www.hzdr.de/publications/Publ-13108
Publ.-Id: 13108


Radiosynthesis of New [90Y]-DOTA-Based Maleimide Reagents Suitable for the Prelabeling of Thiol-Bearing L-Oligonucleotides and Peptides

Schlesinger, J.; Fischer, C.; Közle, I.; Vonhoff, S.; Klussmann, S.; Bergmann, R.; Pietzsch, H.-J.; Steinbach, J.

We describe the radiosynthesis of two new [90Y]-DOTA-based maleimide reagents, suitable for the mild radiolabeling of L-RNAs and peptides modified with thiol-bearing linkers. The synthesis procedure of both maleimide-bearing 90Y complexes, [{(2S)-2-[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzyl]-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl}tetraacetato][90Y]yttrate(1-)([90Y]3) and [{(2S)-2-(4-{[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)butanoyl]amino}benzyl)-1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetrayl]tetraacetato}[90Y]yttrate(1-)([90Y]4), was optimized in terms of an easy purification method via solid-phase extraction (SPE). Application as well as reactivity of both maleimide reagents were initially evaluated by the prelabeling of glutathione (GSH) and a thiol-modified 12mer L-RNA as model substances. In comparison to the N-aryl maleimide-bearing complex [90Y]3, N-alkyl maleimide-bearing complex [90Y]4 showed an increased hydrolytic stability at pH g 7. A slightly higher reactivity was found for [90Y]3 by prelabeling of 0.1 and 1 μg glutathione, respectively, in phosphate buffer (pH 7.2) at room temperature. In terms of very high radiochemical yields, the direct radiolabeling of DOTA-L-RNA conjugate with [90Y]YCl3 proved to be more suitable than the prelabeling of the thiol-modified 12mer L-RNA derivative with [90Y]4.

Permalink: https://www.hzdr.de/publications/Publ-13107
Publ.-Id: 13107


Radiopharmaceutical basic principles of 18F-DOPA in nuclear medicine

Füchtner, F.

kein Abstract verfügbar

  • Invited lecture (Conferences)
    International Congress congenital hyperinsulinism and pancreatic tumors in childhood, 16.-18.09.2009, Greifswald, D

Permalink: https://www.hzdr.de/publications/Publ-13106
Publ.-Id: 13106


Synthesis if new [Y-90]-DOTA based Meleimides for the prelabeling of thiol-bearing L-oligonucleotides and peptides

Pietzsch, H.-J.; Schlesinger, J.; Fischer, C.; Közle, I.; Vonhoff, S.; Klussmann, S.; Bergmann, R.; Steinbach, J.

Objectives: A common chelator for radioisotopes of Y and the lanthanides is DOTA. However, the elevated temperatures necessary to achieve sufficient radiochemical yields may be a drawback, especially for the radiolabeling of thermally sensitive molecules such as DOTA-modified antibodies. A promising alternative to the “direct” radiolabeling of DOTA conjugates (“postlabeling”) is the use of so-called “prelabeling” agents. Here, we present the synthesis of two novel [90Y]-DOTA-based maleimide reagents, [90Y]2 and [90Y]3, suitable for the mild radiolabeling of thiol-bearing peptides or thiol-modified L-RNAs. Application and reactivity of both maleimide reagents were evaluated by the labeling of glutathione (GSH) and a thiol-modified 12mer L-RNA as model substances.
Methods: L‑RNA [sequence: 5’‑(1-hydroxy-7,8-dithia-tetradecyl) UGACUGACUGAC‑3’, MW 4124] was synthesized at NOXXON Pharma AG (Germany). (S)‑p‑NH2‑Bn‑DOTA was purchased from Macrocyclics (USA). 90Y was purchased as [90Y]YCl3 from QSA Global GmbH (Germany). Measurements of 90Y were done in the 90Y channel of a dose calibrator ISOMED 2000 (Nuklear-Medizintechnik Dresden, Germany) by measuring the bremsstrahlung. The compounds were characterized by HPLC, gel electrophoresis and mass spectrometry.
Results: A straightforward method to synthesize [90Y]‑MAD [90Y]2 and [90Y]‑MABD [90Y]3 is to initially complex [90Y]Y3+ with (S)‑p‑NH2‑Bn‑DOTA and to subsequently transform the purified complex [90Y((S)‑p‑NH2‑Bn‑DOTA)]- into the corresponding maleimides by using activating agents. The scheme illustrates the subsequent preparation of [90Y]‑MAD‑GSH and [90Y]‑MABD‑GSH and the 90Y-labeling of an L‑RNA via the pre- and postlabeling approach. In comparison to the N‑aryl maleimide [90Y]‑MAD, N‑alkyl maleimide [90Y]-MABD showed an increased hydrolytic stability at pH ≥ 7. A slightly higher reactivity was found for [90Y]‑MAD by prelabeling of 0.1 and 1 μg glutathione, respectively in phosphate buffer (pH 7.2) at room temperature. In terms of high radiochemical yields, the direct radiolabeling of DOTA-L-RNA with [90Y]YCl3 proved to be more suitable than the prelabeling of the thiol-modified 12mer L-RNA derivative with [90Y]‑MABD.
Conclusions: We could demonstrate the applicability of maleimide reagents [90Y]‑MAD and [90Y]-MABD for the prelabeling approach. Both reagents showed a high potential for that purpose. Concerning high radiochemical yields, the direct labeling of DOTA‑l‑RNA with [90Y]YCl3 proved to be more efficient than the prelabeling of the thiol-modified 12mer l‑RNA with [90Y]‑MABD at low activity levels. With regard to 90Y‑labeling of thermally sensitive molecules prelabeling could have more advantages than the direct radiolabeling, due to the milder labeling conditions.

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S491

Permalink: https://www.hzdr.de/publications/Publ-13105
Publ.-Id: 13105


Imaging of the cell cycle: Synthesis and radiopharmacological evaluation of 124I-labeled CDK4 inhibitors

Köhler, L.; Graf, F.; Bergmann, R.; Steinbach, J.; Pietzsch, J.; Wüst, F.

Objectives: Tumor cells are characterized by their loss of growth control resulting from alterations in regulating pathways of the cell cycle, e.g., a deregulated cyclin dependent kinase (Cdk) activity and/or expression. In 80% of tumors the cell cycle relevant Cdk4-cyclin D1/retinoblastoma (pRb) cascade is altered. Hence, appropriately radiolabeled Cdk4 inhibitors are discussed as promising molecular probes for imaging cell proliferation processes and tumor visualization by PET. This work describes the synthesis and radiopharmacological evaluation of two 124I-labeled Cdk4 inhibitors as potential radiotracers for imaging of Cdk4 in vivo.
Methods: Reference substances and labeling precursors 1 and 2 were prepared with minor modifications according to literature procedures. Radioiodination was performed through regioselective destannylation reaction under mild conditions using [124I]NaI and Iodogen® as the oxidizing agents (Fig. 1). 124I-labeled radiotracers [124I]CKIA and [124I]CKIB were used in cell uptake studies. Biodistribution and small animal PET studies were carried out.
Results: Treatment of a solution containing labeling precursors 1 or 2 (5 mg/ml) with [124I]NaI (29.0 to 275.0 MBq) in Iodogen® precoated tubes gave radiolabeled Cdk4 inhibitors [124I]CKIA and [124I]CKIB in radiochemical yields of up to 35% after removal of Boc protecting group and final HPLC purification. Both compounds were isolated in high radiochemical purity exceeding 95%. The specific radioactivity (As) was 25-35 GBq/μmol at the end of synthesis. The lipophilicity (logP) was determined to be 2.77±0.13 for [124I]CKIA and 1.99±0.03 for [124I]CKIB, respectively. Both compounds remained stable in buffer (PBS, pH 7.4) and ethanol after 24 h at 37°C. In vitro radiotracer uptake studies in human tumor cells using [124I]CKIA showed substantial uptake in adenocarcinoma HT-29 (1264±84 %ID/mg protein) and squamous cell carcinoma FaDu cells (1429±229 %ID/mg protein) after 2 h at 37°C (As:25 GBq/μmol). A significantly lower uptake was detected at 4°C (HT-29: 383±38 %ID/mg protein, FaDu: 437±25 %ID/mg protein). Biodistribution studies of [124I]CKIA and [124I]CKIB showed rapid blood clearance in rats. [124I]CKIA and [124I]CKIB were mainly accumulated and metabolized by liver. Both radiotracers were administered intravenously to mouse FaDu xenograft tumor model and imaging studies were performed on a small-animal PET scanner confirming a high radioactivity concentration in the liver and intestine for both compounds. No radioactivity was found in the brain. PET showed only little uptake of both radiotracers in the tumor.
Conclusions: The radiosynthesis of two 124I-labeled Cdk4 inhibitors has been developed. Both radiotracers were obtained in reproducible radiochemical yields and purity enabling detailed radiopharmacological characterization. Small-animal PET and autoradiography studies showed only low tumor uptake. Further studies are needed to search for more suitable derivatives of these substances as radiotracers for imaging Cdk4 by means of PET.

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S406

Permalink: https://www.hzdr.de/publications/Publ-13104
Publ.-Id: 13104


Pre-clean-up of reaction mixtures in radiopharmaceutical manufacturing by on-line solid phase extraction using HPLC

Füchtner, F.; Mäding, P.; Preusche, S.; Zessin, J.; Steinbach, J.

Objectives: Radiopharmaceuticals are usually synthesised by reaction of simple radiolabeled compounds with a non-radioactive precursor. Afterwards the labeled precursor compound undergoes frequently a deprotection reaction. The resulting reaction mixture is often quite complex and needs HPLC purification to isolate the labeled target compound in high chemical and radiochemical purity. In some cases the composition of the reaction mixture is such complex, that an off-line solid phase extraction (SPE) step is carried out before HPLC purification to separate matrix components and/or interfering solvents. This SPE prepurification of the reaction mixture is difficult to automate and needs special hardware and solvents for rinsing and eluting the SPE cartridge. Additionally, remote controlled synthesis modules become more complex.The general aim of the present work is to develop a process, which allows the pre-cleaning of reaction mixtures from disturbing matrix components by online SPE using HPLC. In detail it results from the need to improve the radiochemical purity of [18F]FDOPA and to reduce the solvent content of dimethylformamide (DMF) during manufacturing of the serotonin transporter radioligand [18F]FMeMcN 5652.
Methods:
The figure shows the scheme of the HPLC hardware, whereas a pre- or guard-column is used as pre-clean-up-column (X) instead of an injection loop. The selectivity of the packing material of both columns (III & X) can be selected in accordance with the separation requirements.The process includes following steps:1. Injection valve (I) in “load position”, The reaction mixture is transferred from the reaction vessel (IX) onto the pre-clean-up-column. The diameter of the packing material of the pre-clean-up-column is in the range, which allows the feeding by gas overpressure. The disturbing matrix components are passed to waste and the target compound is retained.2. The rinsing liquid is filled into the reaction vessel and rinse out the dead volume of the pre-clean-up-column. The target compound is cleaned-up and concentrated.3. Injection valve in “inject position”, The target compound is back flushed out of the pre-clean-up-column onto the separation column (III) by the HPLC mobile phase. The finely purification takes place on the separation column. The eluate is fractionated and the target compound is collected in the common way.For the purification of [18F]FDOPA from the critical radiochemical impurity [18F]fluoride a pre-clean-up-column filled with polymer-based reversed phase (RP) material is used. The finely separation was performed on a silica-based RP column.In case of [18F]FMeMcN 5652 production the clean-up from the solvent, needed for the radiolabeling, and the finely separation is carried out on columns filled with silica-based RP materials.
Results:
...........................................................................[18F]FDOPA............................[18F]FMeMcN
HPLC purification method
...........................................................................[18F]Fluoride [%].....................DMF [mg/ml]
------------------------------------------------------------------------------------------------------------------------------
Injection loop.........................................................7.7 (n=93)..............................1.4 (n=5)
Pre-clean-up-column............................................1.4 (n=25)..............................< 0.001 (n=4)


Conclusions: Using the interlinked on-line SPE / HPLC system, reaction mixtures of radiopharmaceutical synthesis can be cleaned up and disturbing matrix components can be separated from the target compound more efficiently.

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S306

Permalink: https://www.hzdr.de/publications/Publ-13103
Publ.-Id: 13103


Direct labeling of peptides with [18F]FDG

Hultsch, C.; Bergmann, R.; Berndt, M.; Wüst, F.

Objectives: The routine 18F labeling of biomacromolecules like peptides and proteins mainly exploits the use of bifunctional labeling precursors, also referred to as prosthetic groups. 2-[18F]Fluoro-2-deoxy-D-glucose ([18F]FDG) is the most important clinical PET radiotracer, but only very few examples using readily available [18F]FDG as a building block for the radiosynthesis of 18F-labeled compounds. The present study describes the use of [18F]FDG as a 18F building block for the direct labeling of various aminooxy-functionalized peptides via chemoselective oxime formation. The potential of this novel peptide labeling reaction was expemplified by means of various neurotensin NT(8-13) derivatives.
Methods: The labeling reaction was performed using a 0.9% NaCl solution of [18F]FDG and aminooxy-functionalized peptide at different concentrations in a mixture of MeOH/H2O at 80 °C for 30 min. The reaction mixture was analyzed by radio-HPLC to determine the radiochemical yield of the conjugation reaction (Fig. 1).
Results: Direct labeling of aminooxy-functionalized peptides with [18F]FDG was strongly dependent on the amount of used peptide. Monomeric NT(8-13) derivative gave best radiochemical yields of up to 80% based upon [18F]FDG. More complex dimeric and tetrameric neurotensin derivatives gave lower radiochemical yields at comparable peptide concentrations. Increase of [18F]FDG activity also lowered radiochemical yield due to an increasing competitive reaction with glucose originating from the [18F]FDG solution. Depending on the size of the used peptide, separation of [18F]FDG-labeled peptide from glucose-labeled peptide is possible by semi-preparative HPLC. The formation of isomers during the aminooxy-aldehyde conjugation reaction between [18F]FDG and aminooxy-functionalized peptides in aqueous media leads to the formation of isomers according to literature reports.
Conclusions: For the first time, readily available PET radiotracer [18F]FDG was shown to be a suitable prosthetic group for direct labeling of aminooxy-functionalized peptides with fluorine-18 under mild conditions. The reaction is especially suitable for small peptides. However, application of larger peptides seems to be limited by increasing separation difficulties of the corresponding glucose-peptide conjugate.

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S145

Permalink: https://www.hzdr.de/publications/Publ-13102
Publ.-Id: 13102


Fluorine-18 Labeling of Phosphorpeptides: A convenient Approach for the Evaluation of Phosphorpeptide Metabolism in vivo

Richter, S.; Bergmann, R.; Steinbach, J.; Pietzsch, J.; Wüst, F.

Objectives: Phosphopeptides are very useful reagents to study signal transduction pathways related with cellular protein phosphorylation/dephosphorylation. Phosphopeptides also have been identified as important drug candidates to both inhibit and stimulate intracellular signaling mechanisms through targeting phosphotyrosine, phosphoserine or phosphothreonine residue-binding protein domains. In this work we describe a convenient method for the mild and sufficient radiolabeling of phosphopeptides with the short-lived positron emitter fluorine-18 to allow radiopharmacological studies on phosphopeptide metabolism in vivo by means of positron emission tomography (PET).
Methods: Peptide syntheses were performed on peptide synthesizer (Syro I, MultiSynTech, Germany) using standard Fmoc chemistry. Radiolabeling was accomplished via conjugation of the N-terminus of Polo-box domain (PBD)-binding phosphopeptide H-Met-Gln-Ser-pThr-Pro-Leu-OH 1 and its unphosphorylated analog 2 with the bifunctional labeling agent N-succinimidyl-p-[18F]fluorobenzoate ([18F]SFB) (Fig. 1).
The radiolabeled phosphopeptide [18F]FB-Met-Gln-Ser-pThr-Pro-Leu-OH [18F]-1 and its unphosphorylated analog [18F]FB-Met-Gln-Ser-Thr-Pro-Leu-OH [18F]-2 were subjected to radiopharmacological evaluation involving investigation of metabolic stability in vitro and in vivo, cell uptake studies in human adenocarcinoma (HT-29) and squamous cell carcinoma (FaDu) cell lines, and small-animal PET studies in Wistar rats and NMRI nu/nu HT-29 tumor-bearing mice.
Results: Radiolabeling was achieved via 18F-fluorobenzoylation using the Bolton-Hunter-type reagent N-succinimidyl-p-[18F]fluorobenzoate ([18F]SFB). The optimized radiosynthesis was conducted in a 0.05 M Na2HPO4 buffer solution (pH 9.0) at 40°C within 30 min using low amounts of peptide precursor (0.5 mg) to afford reproducible radiochemical yields (25-29%) and high radiochemical purity (>98%) within 95-109 min including HPLC purification. Cell uptake studies in HT-29 and FaDu tumor cells revealed only very little radiotracer uptake (less than 0.6% ID/mg protein). Radiolabeled phosphopeptide [18F]-1 showed remarkable high metabolic stability in vivo (65% intact peptide after 20 min) compared to the corresponding unphosphorylated peptide [18F]-2 (<5% intact peptide after 20 min). A detailed discussion on the radiopharmacological profile in vitro and in vivo of peptides [18F]-1 and [18F]-2 will be presented.
Conclusions: We developed a reproducible synthesis for 18F-labeled phosphopeptides, and the presented method is a promising approach for studying phosphopeptide metabolism and kinetics in vivo. Furthermore, cell penetrating peptides (CPP) are currently under investigation as potential mediators to enhance cell uptake of the desired 18F-labeled phosphopeptides.

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S144

Permalink: https://www.hzdr.de/publications/Publ-13101
Publ.-Id: 13101


Radiofluorination via Staudinger Ligation

Mamat, C.; Pretze, M.; Steinbach, J.; Wüst, F.

Objectives: The chemical labeling of biomolecules continues to be an important tool for the study of the cellular fate.[1] In particular the introduction of 18F into higher molecular weight compounds like peptides, proteins, oligonucleotides or antibodies represents a special challenge. Usually they can not be labelled with 18F at high specific activity directly due to the rough reaction conditions. To circumvent this problem prostetic groups were used for 18F labeling of peptides and proteins. Therefore 18F labeled small organic molecules were synthesised capable of being linked to peptides, proteins or antibodies under mild conditions. Only a handful of reactions are known for the selective introduction of these labeling agents.
Methods: Although several bioconjugation techniques are available for preparation of bioconjugates substituted with a limited number of functional groups, truly chemoselective ligation reactions are rather limited. Most ligation reactions rely on the reaction of an electrophile with a nucleophile. As biological systems are rich in diverse electrophilic and nucleophilic sites, only a few functional groups are available that exhibit orthogonal reactivity to the functional groups present. Bioorthogonal reactions like the [3+2] Huisgen cycloaddition[3] were applicated for the selective radiolabeling[4] of biomolecules. The Staudinger Ligation introduced by Saxon and Bertozzi[5] exploits the smooth reaction between an azide and a phosphane to form an amide bridge between the labeling agent and the respective biomolecule.
Results: Substituted phosphanes were used as synthons for the Staudinger Ligation. The preparation of these compounds succeeds via Pd-catalyzed P-C cross coupling of iodophenyl benzoates with HPPh2. No extensive protection group chemistry is needed for this coupling reaction.[2] The radiofluorination proceeds under standard conditions and the subsequent ligation reaction occurs under mild conditions (20 min, 50 watt microwave) that affords the respective Staudinger products in high yields.
Conclusions: Our first promising results show the potential of this labeling method for the radiofluorination of various organic model compounds and biomolecules. The experimental details will be presented.

References: [1] J. A. Prescher, C. R. Bertozzi, Nature Chem. Biol. 2005, 1, 13-21. [2] C. Mamat, A. Flemming, M. Kckerling, J. Steinbach, F. R. Wuest, Eur. J. Org. Chem. 2009, submitted. [3] C. Mamat, T. Ramenda, F. R. Wuest, Mini-Rev. Org. Chem. 2009, 6, 21-34. [4] T. Ramenda, R. Bergmann, F. Wuest, Lett. Drug Design Disc. 2007, 4, 279-285. [5] K. L. Kiick, E. Saxon, D. A. Tirrell, C. R. Bertozzi, Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 19-24.

  • Poster
    18th International Symposium of Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S142

Permalink: https://www.hzdr.de/publications/Publ-13100
Publ.-Id: 13100


Synthesis and Radiopharmacological Evaluation of 18F-labeled Bombesin Analog [18F]BX-00374436 for Imaging of GRP Receptor-Expression Prostate Cancer

Ramenda, T.; Bergmann, R.; Friebe, M.; Borkowski, S.; Srinivasan, A.; Dinkelborg, L.; Pietzsch, J.; Steinbach, J.; Wüst, F.

Objectives: Over the last two decades, radiolabeled peptides have been widely used as promising radiotracers for tumor targeting. In recent years, bombesin and bombesin analogs have attracted much attention as high affinity and selectivity ligands for the gastrin-releasing peptide (GRP) receptor. The GRP receptor was found to be overexpressed and implicated in a variety of human tumors. Radiolabeled bombesin and bombesin analogs represent an interesting class of diagnostic probes for molecular imaging of GRP receptor-expressing prostate cancer. This work is aimed at the development of an 18F-labeled bombesin analog for molecular imaging GRP receptors in prostate cancer xenografts.
Methods: Aminopentanoic acid-modified bombesin analog BX-06053011 was conjugated with the bifunctional labeling agent N-succinimidyl-4-[18F]fluorobenzoate ([18F]SFB) in borate buffer (pH = 8.2) for 30 min at 50 °C to give the desired 18F-labeled bombesin analog [18F]BX-00374436 (Fig. 1). Tumor-targeting of radiolabeled bombesin analog [18F]BX-00374436 was evaluated in male nude mice bearing human prostate cancer (PC3) by means of biodistribution and dynamic small animal PET studies.
Results: 18F-labeled bombesin analog [18F]BX-00374436 was prepared in 30% radiochemical yield (based upon [18F]SFB) within 80 min including HPLC purification, evaporation of HPLC eluent and formulation in 0.9% saline. The radiochemical purity exceeded 95%, and the specific activity was 20 GBq/μmol. The binding affinity (KD) of fluorobenzoylated bombesin BX-00374436 was determined to be 0.7 nM. Radiotracer [18F]BX-00374436 showed reasonable metabolic stability in mouse blood, being 65% of intact radiolabeled peptide after 60 min. Tumor uptake of [18F]BX-00374436 in PC3 tumor bearing nude mice was 2.75 %ID/g after 5 min p.i., and 2.45 %ID/g after 60 min p.i. The receptor specificity of radiotracer [18F]BX-00374436 could be demonstrated by effective blocking of tumor uptake in the presence of non-radioactive BX-00374436. Dynamic small animal PET imaging confirmed specific radiotracer uptake in the PC3 tumor.
Conclusions: The present study showed that 18F-labeled bombesin analog [18F]BX-00374436 is a suitable radiotracer for molecular imaging of GRP receptor-positive prostate cancer by means of PET.

  • Lecture (Conference)
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S29

Permalink: https://www.hzdr.de/publications/Publ-13099
Publ.-Id: 13099


Labelling of Proteins with Fluorine-18 via Click Chemistry

Ramenda, T.; Knieß, T.; Steinbach, J.; Wüst, F.

Objectives: The radiolabeling of peptides and proteins with the short-lived positron emitter 18F requires rapid and mild reaction conditions compatible with the structural and functional integrity of these biomolecules. Over the last two years several approaches have been published focusing on the application of copper(I)-mediated 1,3-dipolar [3+2]cycloaddition of azides and alkynes for labeling peptides with 18F. However, to date no 18F labeling of proteins via click chemistry has been reported. In this work we describe for the first time the application of click chemistry for 18F labeling of proteins as exemplified with azide-functionalized human serum albumin (HSA). Click chemistry was accomplished through 4-[18F]fluoro-N-methyl-N-(prop-2-ynyl)benzenesulfonamide (p[18F]F-SA) as novel alkine-containing 18F-labeled click chemistry building block.
Methods: The novel click chemistry building block p[18F]F-SA was prepared in a single step reaction in a remotely controlled synthesis module starting from readily available labeling precursor (Fig. 1).
HSA was modified with azide residues through conjugation of the lysine residues in HSA with an azide-functionalized active ester. Azide-modified HSA was subjected to digest with three different endoproteinases and subsequent MALDI-TOF MS analysis to assess the number of introduced azide residues. Radiolabeling of modified HSA was accomplished with p[18F]F-SA in the presense of Cu(I)Br and the Cu(I) chelating ligand tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA). Radiolabeled HSA was purified with size-exclusion chromatography and analyzed with SDS-PAGE.
Results: Radiolabeled sulfonamide p[18F]F-SA could be obtained in an automated synthesis unit in radiochemical yields of 21-35% (decay-corrected) within 75 min after HPLC purification. The radiochemical purity was >99%, and the specific activity was in the range of 71-128 GBq/μmol. Sulfonamide p[18F]F-SA showed favorable lipophilicity (logP = 1.6) allowing application in aqueous reaction media. Tryptic digest and subsequent MALDI-TOF MS analysis of modified HSA revealed the introduction of an average of 28 azide residues into HSA. Click chemistry of azide-functionalized HSA (0.5 mg) with CuBr (0.2 mg) and TBTA in phosphate buffer (pH 7.4) gave 31% of 18F-labeled HSA after size-exclusion chromatography.
Conclusions: The convenient radiosynthesis of p[18F]F-SA as a novel 18F-labeled sulfonamide-based click chemistry building block in an automated synthesis unit allows its wide application for a broad range of click chemistry reactions. For the first time, click chemistry could successfully be applied to the 18F labeling of proteins, which further expands the scope of click chemistry as versatile tool for radiolabeling reactions.

  • Lecture (Conference)
    18th International Symposium on Radiopharmaceutical Scieneces, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S25

Permalink: https://www.hzdr.de/publications/Publ-13098
Publ.-Id: 13098


Synthesis of a potential tyrosine kinase inhibitor by knoevenagel condensation of oxindole with 4-[18F]Fluorbenzaldehyde

Knieß, T.; Kuchar, M.; Steinbach, J.; Wüst, F.

Objectives: Receptor tyrosine kinases (RTKs) play an important role in tumour angiogenesis through their involvement in proliferation, migration and differentiation between tumour and endothelial cells. Recently, small molecule tyrosine kinase inhibitors like Imatinib mesylate (Gleevec®), Gefitinib (Iressa®) and SU11248 (Sutent®) have been radiolabelled to study tumour angiogenesis in vivo1,2,3. The aim of the present work is the development of an sufficient radiosynthesis of 3-(4’-[18F]fluoro-benzylidenyl]-indolin-2-one 2 as derivative of potent RTK inhibitor Semaxinib® based on Knoevenagel condensation of 4-[18F]fluorobenzaldehyde with oxindole.
Methods: Synthesis of 4-[18F]fluorobenzaldehyde was performed by reacting [18F]fluoride with 4-trimethylammoniumbenzaldehyde triflate in an automated synthesis module (Nuclear Interface). Briefly, 15 mg of precursor dissolved in acetonitrile (1 ml) was heated with dried [18F]KF at 90 °C for 10 min. After addition of water (11 ml), 4-[18F]fluorobenzaldehyde was purified via solid-phase extraction on a HLB-plus cartridge (250 mg, Waters). Purified 4-[18F]fluorobenzaldehyde was eluted from the cartridge with ethanol (3 ml) and transferred into a separate reaction vial containing oxindole 1 (10 mg) and a base. Knoevenagel condensation occurred at 90 °C for 20 min (Fig. 1). The radiochemical yield of product 2 was determined by radio-HPLC.

Results: Knoevenagel condensation of oxindole 1 with 4-[18F]fluorobenzaldehyde was optimised by screening the influence of different bases on the radiochemical yield (RCY) of the carbonyl olefination reaction. The results are summarised in Table 1. Knoevenagel condensation strongly depends on the used base. Best results could be obtained by using amine bases piperidine (18% to 29%) or diethylamine (48%). Application of stronger amine bases (DABCO, diisopropyl-ethyl amine) or weaker bases (ammonium acetate, 2,6-di-tert.-butyl pyridine) resulted in lower or no product formation. Phosphazane as a very strong base yielded 26% of desired product 2 along with formation of large amounts of non-identified side products.

Table 1. Knoevenagel condensation between 4-[18F]fluorobenzaldehyde and oxindole

Conclusions: Knoevenagel condensation of 4-[18F]Fluorobenzaldehyde with oxindole is a suitable labelling technique for the synthesis of radiotracer 2. Within a series of different bases, diethylamine provides highest radiochemical yields of up to 48%. The Knoevenagel condensation reaction optimised under the object of radiolabeling involving readily available 4-[18F]Fluorobenzaldehyde should be applicable for the convenient radiosynthesis of other compounds containing a benzylidene motif.

References: [1] Kil KE et al. Nucl Med Biol, 2007, 34, 153. [2] Wang JQ et al. Bioorg Med Chem Lett, 2006, 16, 4102. [3] Wang JQ et al. Bioorg Med Chem Lett, 2005, 15, 4380.

Keywords: 4-[18F]fluorobenzaldehyde; tyrosine kinase inhibitor; Knoevenagel condensation

  • Poster
    18th International Symposium on Radiopharmaceutical Sciences, 12.-17.07.2009, Edmonton, Canada
  • Abstract in refereed journal
    Journal of Labelled Compounds and Radiopharmaceuticals 52(2009)Suppl 1, S.182

Permalink: https://www.hzdr.de/publications/Publ-13097
Publ.-Id: 13097


MnSi1.7 nanoparticles embedded in Si: Superparamagnetism with collective behavior

Zhou, S.; Shalimov, A.; Potzger, K.; Helm, M.; Fassbender, J.; Schmidt, H.

The doping of Mn in Si is attracting research attentions due to the possibility to fabricate Si-based diluted magnetic semiconductors. However, the low solubility of Mn in Si favors the precipitation of Mn ions even at nonequilibrium growth conditions. MnSi1.7 nanoparticles are the common precipitates, which show exotic magnetic properties in comparison with the MnSi1.7 bulk phase. In this paper we present the static and dynamic magnetic properties of MnSi1.7 nanoparticles. Using the Preisach model, we derive the magnetic parameters, such as the magnetization of individual particles, the distribution of coercive fields and the interparticle interaction field. Time-dependent magnetization measurements reveal aging and memory effects, qualitatively similar to those seen in spin glasses.

Keywords: ageing; coercive force; elemental semiconductors; magnetic anisotropy; magnetic particles

Permalink: https://www.hzdr.de/publications/Publ-13096
Publ.-Id: 13096


The effects of surface tension on flooding in counter-current two-phase flow in an inclined tube

Deendarlianto; Ousaka, A.; Indarto; Kariyasaki, A.; Lucas, D.; Vierow, K.; Vallee, C.; Hogan, K.

The purpose of the present study is to investigate the effects of surface tension on flooding phenomena in counter-current two-phase flow in an inclined tube. Previous studies by other researchers have shown that surface tension has a stabilizing effect on the falling liquid film under certain conditions and a destabilizing or unclear trend under other conditions. Experimental results are reported herein for air-water systems in which a surfactant has been added to vary the liquid surface tension without altering other liquid properties. The flooding section is a tube of 16 mm in inner diameter and 1.1 m length, inclined at 30 to 60 degree from horizontal. The flooding mechanisms were observed by using two high-speed video cameras and by measuring the time variation of liquid hold-up along the test tube. The results show that effects of surface tension are significant. The gas velocity needed to induce flooding is lower for a lower surface tension. There was no upward motion of the wave upon flooding occurrence, even for lower a surface tension. Observations on the liquid film behavior after flooding occurred suggest that the entrainment of liquid droplets plays an important role in the upward transport of liquid. Finally, an empirical correlation is proposed that includes functional dependencies on surface tension and tube inclination.

Keywords: Counter-current two-phase flow; Flooding; Inclined tube; Surface tension; Flooding mechanisms

Downloads:

Permalink: https://www.hzdr.de/publications/Publ-13095
Publ.-Id: 13095


Nanopatterning of Si surfaces by normal incident ion erosion: Influence of iron incorporation on surface morphology evolution

Zhou, J.; Facsko, S.; Lu, M.; Möller, W.

The surface morphology of Si(100) induced by 1200 eV Ar+ ion bombardment at normal incidence with and without Fe incorporation is presented. The formation of nanodot patterns is observed only when the stationary Fe areal density in the surface is above a threshold value of 8×1014 cm-2 . This result is interpreted in terms of an additional surface instability due to locally nonuniform sputtering in connection with the presence of a Fe rich amorphous phase at the peak of the nanodots. At Fe concentrations below the threshold, smoothing dominates and pattern formation is inhibited. The transition from a k-2 to a k-4 behavior in the asymptotic power spectral density function supports the conclusion that under these conditions ballistic smoothing and ion-enhanced viscous flow are the two dominant mechanisms of surface relaxation.

Keywords: dot patterns; ion sputtering; silicon; metal incorporation

Permalink: https://www.hzdr.de/publications/Publ-13094
Publ.-Id: 13094


Pages: [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] [47] [48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60] [61] [62] [63] [64] [65] [66] [67] [68] [69] [70] [71] [72] [73] [74] [75] [76] [77] [78] [79] [80] [81] [82] [83] [84] [85] [86] [87] [88] [89] [90] [91] [92] [93] [94] [95] [96] [97] [98] [99] [100] [101] [102] [103] [104] [105] [106] [107] [108] [109] [110] [111] [112] [113] [114] [115] [116] [117] [118] [119] [120] [121] [122] [123] [124] [125] [126] [127] [128] [129] [130] [131] [132] [133] [134] [135] [136] [137] [138] [139] [140] [141] [142] [143] [144] [145] [146] [147] [148] [149] [150] [151] [152] [153] [154] [155] [156] [157] [158] [159] [160] [161] [162] [163] [164] [165] [166] [167] [168] [169] [170] [171] [172] [173] [174] [175] [176] [177] [178] [179] [180] [181] [182] [183] [184] [185] [186] [187] [188] [189] [190] [191] [192] [193] [194] [195] [196] [197] [198] [199] [200] [201] [202] [203] [204] [205] [206] [207] [208] [209] [210] [211] [212] [213] [214] [215] [216] [217] [218] [219] [220] [221] [222] [223] [224] [225] [226] [227] [228] [229] [230] [231] [232] [233] [234] [235] [236] [237] [238] [239] [240] [241] [242] [243] [244] [245] [246] [247] [248] [249] [250] [251] [252] [253] [254] [255] [256] [257] [258] [259] [260] [261] [262] [263] [264] [265] [266] [267] [268] [269] [270] [271] [272] [273] [274] [275] [276] [277] [278] [279] [280] [281] [282] [283] [284]