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Flüssigmetallbatterien als Option für elektrische Großspeicher
Nimtz, M.; Landgraf, S.; Personnettaz, P.; Weber, N.; Weier, T.
Der Bedarf an kostengünstigen Großspeichern für elektrische Energie wird zukünftig, bei zunehmendem Ausbau der erneuerbaren Energien, wachsen. Derzeit vorhandene Technologien (im wesentlichen Lithium-Ionen bzw. Blei-Säure Batterien) bieten bis in den Bereich von etwa 10 bis 30 MW bzw. MWh eine anwendungsbereite Speicherform.
Hauptanwendungsfeld ist hierbei zurzeit die Primärregelenergie, da dort vergleichsweise kleine Entladetiefen und nur wenige Vollzyklen auftreten. Ein Einsatz als Speicher im Stunden- oder gar Mehrtagesbetrieb kann von diesen Technologien jedoch meist nicht erbracht werden, da die Alterung der Zellen bei hohen Entladetiefen (ΔSOC > 50%) stark zunimmt und dementsprechend die Kapazität der Zellen bereits nach wenigen Jahren stark abnimmt.
Flüssigmetallbatterien  bieten eine Alternative zu den vorgenannten Technologien, wobei der Fokus hier auf dem Einsatz als Großspeicher (>>1 MWh) liegt. In Flüssigmetallbatterien liegen alle Aktivmaterialien in flüssiger Form vor. Alterungseffekte, die auf einer Schädigung oder auf der Degeneration der Elektrodenmaterialien beruhen, werden hier nicht erwartet. Prognostizierte Vollzyklenzahlen liegen im Bereich von 105 Vollzyklen, was die Flüssigmetallbatterien auch für den Einsatz abseits der Primärregelung interessant macht. Weitere Vorteile sind der einfache Aufbau, gute Skalierbarkeit und die leichte Wiederaufbereitung der verwendeten Materialien.
Der Beitrag stellt die Technologie, die Einsatzmöglichkeiten und Parameter sowie die Forschungsaktivitäten am Helmholtz-Zentrum Dresden-Rossendorf  vor. Schwerpunkt ist die Darstellung der neu entwickelten Software „LMB-System-Calculator“, welche eine integrierte Auslegung, Modellierung und Simulation von Flüssigmetallbatterien in Hinblick auf geometrische (siehe Abb. 1), elektrische und thermische Größen erlaubt.
Keywords: Flüssigmetallbatterie; Energiespeicher; Modellierung; Simulation; Liquid metal battery; energy storage; modelling; simulation
51. Kraftwerkstechnisches Kolloquium, 22.-23.10.2019, Dresden, Deutschland
Contribution to proceedings
51. Kraftwerkstechnisches Kolloquium, 22.-23.10.2019, Dresden, Deutschland
Kraftwerkstechnik 2019 - Power PLant Technology, Freiberg: Saxonia, 978-3-934409-93-4, 677-686
An eurlerian-eulerian CFD approach to simulate the thermaohydrulics of piipes, channel or rod bundles: from onset of nucleate boiling to CHF
Ding, W.; Krepper, E.; Hampel, U.
The Eulerian-Eulerian computational fluid dynamics (CFD) approach is widely applied in the simulation of industrial scale thermal fluid dynamics problems, such as flow and heat transfer in fuel elements. However, the case dependency of submodels in the Eulerian-Eulerian CFD approach currently hampers its applicability. In order to reduce this dependency, a submodel to predict the bubble departure in both pool and flow boiling was developed in our group, which includes the impact of microlayer, thermal diffusion, condensation and force balance. Moreover, we also developed a new CHF- concept. It is currently based on correlations but we are continuously working on a transition to a fully physics-based model, which e.g. considers the dependency of boiling on the microlayer thickness, bubble base expansion speed and local shear stress. In order to implement the bubble dynamics model and CHF- model into the Eulerian-Eulerian CFD framework, a new cavity activation and heat partitioning model was developed, which is not only used for bubble nucleation but also connects the nucleate boiling and CHF- in one CFD approach. However, nucleation site density is strongly dependent on the surface properties, which is difficult to model without correlations.
Keywords: CFD; Wall boiling; CHF
18th International Topical Meeting on Nuclear Reactor Thermal Hydraulics (NURETH-18), 18.-22.08.2019, Portland, USA
Critical heat flux as a mass flux dependent phenomenon: Theoretical analysis, experimental confirmation and further CFD application
Ding, W.; Geißler, T.; Krepper, E.; Hampel, U.
In this work, we report on a theoretical analysis and experimental investigations on critical heat flux (CHF) in subcooled flow boiling firstly. Commonly, CHF is considered as a local phenomenon. A validated CHF- concept recently developed in our group indicated that CHF may be initiated in two different ways, that is, locally and globally. We designed and conducted an experiment to verify this hypothesis. The experimental results agree well with the expectations from our CHF- modelling and confirm the two mechanisms. Following that, we continued to clarify the role of different parameters, such as channel orientation, channel length and hydraulic diameter. The new concept of CHF is useful to explain and predict CHF at conditions of low pressure and low fluid velocity. Further we applied this concept into an Euler-Euler computational multiphase fluid dynamics (CMFD) approach with wall boiling model which successfully predict the critical volume fraction under different conditions. The simulation results also had a good agreement with the corresponding experimental results.
Keywords: Critical heat flux; Boiling; CMFD
Invited lecture (Conferences)
9th China-Korea Workshop on Nuclear Reactor Thermal-Hydraulics (WORTH-9), 15.-18.05.2019, Chongqing, China
10th International Conference on Multiphase Flow, 19.-24.05.2019, Rio de Janeiro, Brazil
Pulse-front tilt in laser-plasma accelerators with short focal lengths
Laser ion accelerators utilize high-power laser pulses in tight-focusing geometries to provide pulsed, high-intensity ion beams. Efficient capturing, transport and application of these beams is an ongoing effort which depends on precise knowledge of the accelerated ion distribution's properties and how to control these. For example, it is known that the propagation direction of the accelerated ions can be controlled by tilting the driving laser pulse-front. Since laser pulse-front tilts can be present accidentally, for example by a small misalignment of the compressor gratings in a chirped-pulse amplification system, knowledge of the scaling of the pulse-front tilt at a target position is desired. The talk gives relations for pulse-front orientation dependent on setup parameters and identifies regimes were pulse-front tilt has a sizable impact.
Keywords: Pulse-front tilt; high-power laser
DPG-Frühjahrstagung, 17.-22.03.2019, München, Deutschland
Flüssigmetallbatterien als Großspeicher - Technologie, Scale-Up und Optionen zur Sektorkopplung
Es werden die grundsätzlichen Eigenschaften von Flüssigmetallbatterien beschrieben sowie Methoden und Ergebnisse zum Scale-Up vorgestellt. Des weiteren werden Funktionsweise und Anwendung der LMB-System-Calculator Software erläutert sowie Anwendungsoptionen für Flüssigmetallbbatterien, insbesondere bei der Sektorkoppelung vorgestellt.
Basic properties of Liquid Metal Batteries are described and methods and results for scale-up calculations are presented.
Also, functioning and usage of the LMB-System-Calculator software are discussed and options for the operation of Liquid Metal Batteries, especially for the sector-coupling are presented.
Keywords: LMB; Flüssigmetallbatterien; Scale-Up; Speicher; Sektorkoppelung; LMB; liquid metal battery; scale-up; storage; sectro-coupling
Energie System 2050 Forschungsthema 1, 1. Workshop 2019, 19.-20.03.2019, Karlsruhe, Deutschland
Chemistry and accelerator mass spectrometry – A life happily ever after?
Accelerator mass spectrometry (AMS) is the most sensitive analytical method to measure long-lived radionuclides. The detection limits are generally several orders of magnitude better, i.e. as low as 10-16 (radionuclide/stable nuclide), than any other mass spectrometry or decay counting method. AMS needs smaller sample sizes and measurements are finished within a few minutes to hours.
However, it is often forgotten that research projects applying AMS start with taking appropriate samples, followed by labour- and cost-intensive sample preparation. The goal can easily be described as “making the big samples (up to several kg’s) to fit in an AMS target holder (< 10 mg)”. This includes getting rid of the matrix and the troublesome isobars. By technical improvements of AMS leading to lower detection limits or better mass-and-element discrimination, sample masses can be reduced to gram-quantities instead of kg’s allowing easier, faster, and cheaper chemistry. Recent AMS developments also address very efficiently isobar elimination.
Nevertheless, some samples can contain different sources of the radionuclide-of-interest such as ¹⁰Be produced in the Earth’s atmosphere polluting the ¹⁰Be of interest produced in-situ in quartz. Hence, in this case chemistry is inevitable for cleaning the samples from the contamination. Another “mission” of chemistry might be the reduction of corresponding stable nuclides, e.g. 35,37Cl, ²⁷Al, natFe by preceding cleaning or by gentle leaching to enhance the radionuclide/stable nuclide ratio or to minimize interfering nuclear reactions such as thermal-neutron capture on ³⁵Cl. When applying isotope-dilution AMS to simultaneously determine the natCl content of a sample, which is an absolute requirement for surface exposure dating of Ca- or K-rich minerals, chemical sample preparation is also mandatory.
As the majority of research projects involving AMS is of true interdisciplinary character, knowledge of sample preparation is usually passed-on to (young) non-chemists. These are trained learning-by-doing to perform the chemical preparation of their own samples. Therefore, the development of “routine” AMS sample preparation needs to have a strong focus on safety and easy-to-be-trained aspects with the least opportunity for failure.
In conclusion, although new AMS technical developments for isobar suppression like the laser-negative ion interaction system at VERA promise to reduce elaborate chemistry in some cases, we should keep in mind that chemical knowledge will always be needed for a lot of interdisciplinary research projects.
VERA-Seminar, Institut für Isotopenphysik, Universität Wien, 28.03.2019, Wien, Österreich
Li-containing liquid metal alloy ion sources for focused-ion beam instrumentation
Mazarov, P.; Nadzeyka, A.; Richter, T.; Yu, Y.; Sanabia, J. E.; Bischoff, L.; Hlawacek, G.; Pilz, W.; Klingner, N.
Focused Ion Beams (FIB) gain an increasing interest in the field of nanotechnology particular for prototyping of microelectronic devices, patterning of 2D materials, high resolution imaging or high resolution ion lithography1. Concerning ion beam resolution and minimization of unwanted damage, light ions like He or Li are preferred candidates. Liquid metal alloy ion sources (LMAIS) with a life time of more than 1000 µAh on the basis of Ga35Bi60Li5 and Sn95Li5 alloys were developed, characterized and finally applied in a commercial mass-separated VELION FIB-SEM system (Raith GmbH). The resolution for imaging and also for the formation of nanostructures using a thin gold film was determined.
In the case of Li ions from the mass separated FIB a lateral resolution of 5.6 nm could be obtained in first experiments2 and the sputter yield was determined to 0.4 for 35 keV Li ions on Au. For reference, the helium ion microscope (HIM) has a lateral resolution of about 0.5 nm and 1.8 nm, for He and Ne respectively, He has a sputter yield of 0.13. For sub-10 nm focused ion beam nanofabrication and microscopy, the GaBiLi-FIB or the SnLi-FIB could therefore be considered alternatives to the HIM with the benefit of providing additional ion species in a mass separated FIB without changing the ion source.
1 L. Bischoff et al. Appl. Phys. Rev. 3, 021 101 (2016).
2 W. Pilz et al. J. Vac. Sci. Technol. B A-18-399 (submitted, 2018).
3 G. Hlawacek et al. J. Vac. Sci. Technol. B 32, 020 801 (2014).
The 63rd International Conference On ELECTRON, ION, AND PHOTON BEAM TECHNOLOGY AND NANOFABRICATION, 28.-31.05.2019, Minneapolis, United States of America
SiCxNy:Fe films as a tunable ferromagnetic material with tailored conductivity
Pushkarev, R.; Fainer, N.; Kirienko, V.; Matsynin, A.; Nadolinnyy, V.; Merenkov, I.; Trubina, S.; Ehrenburg, S.; Kvashnina, K.
Amorphous ferromagnetic materials with the variable composition are promising candidates for application in rapidlygrowing technological fields, such as spintronics. However, the significant downside of current state-of-art materials is a conductivity mismatch between injector and semiconductor which often is associated with the unavailability to control and precisely tailor magnetic properties and conductivity. We report on the synthesis of soft-magnetic SiCxNy:Fe films with the saturation magnetization of 20 e.m.u./cm3 and conductivity similar to the one of Si, which is crucial for possible applications.
XRD with synchrotron radiation and EXAFS revealed the complex composite structure of the films: crystals of Fe3Si, Fe5Si3, SiC and graphite are embedded into the amorphous matrix of SiCxNy. The variation of deposition conditions allowed us to separately control the magnetic properties through the iron concentration and the conductivity of the material through the amorphous SiCxNy matrix composition. The reported results revealed a significant potential of SiCxNy:Fe films as a prospective object for analysis of spin-polarized transport in amorphous semiconductors and for application in field of spintronics.
Journal of Materials Chemistry C 7(2019), 4250-4258
- Final Draft PDF 875 kB Secondary publication
Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening
Haldar, R.; Batra, K.; Marschner, S. M.; Kuc, A. B.; Zahn, S.; Fischer, R. A.; Bräse, S.; Heine, T.; Wöll, C.
In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and the Soret bands can be done using a computational approach where substitution patterns are optimized in silico. The Most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow using the PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were additionally able to exploit packing effects resulting in pronounced red shifts, which allowed to further optimizing the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating a huge potential of computational screening methods in the tailoring of MOF and SURMOF photophysical properties.
Chemistry - A European Journal 25(2019)33, 7847-7851
- Final Draft PDF 2,9 MB Secondary publication
Synthesis and Functionalization of Radium-doped Barium Sulfate Nanoparticles
The radionuclides radium-223 and radium-224 are two alpha-emitting radionuclides with suitable properties for the TAT. To this date, radium-223 in form of [223Ra]radium chloride (Xofigo) is the only EMA and FDA approved alpha-emitting radiopharmaceutical. Due to its calcimimetic behavior, the radium ion is a bone-seeking therapeutic. To extend the radiopharmaceutical potential of both radionuclides, novel carrier systems have to be developed. Therefore, it is appropriate to investigate different kinds of nanoparticles for their ability to transport radium. Especially, a barium sulfate matrix seems to be sufficient since the principle of co-precipitating the sulfates of radium and barium allows an easy and fast synthesis of radium-doped nanoparticles. Beyond the incorporation of alpha-emitting radionuclides like radium-223 and radium-224, the homologue radionuclide barium-131 can be incorporated as well. Barium 131 decays by electron capture and provides suitable properties for diagnostic applications in nuclear medicine. Radium-223/-224 and barium-131 form a matched pair for new theragnostic approaches. In our research group, we are developing simple methods for the synthesis of small radiolabeled radium/barium sulfate nanoparticles. Furthermore, we are investigating suitable surface functionalizations to attach biological targeting moieties.
Keywords: Bariumsulfat; Radium-224; Nanopartikel
11th International Symposium on Targeted-Alpha-Therapy, 01.-06.04.2019, Ottawa, Kanada
Abstract in refereed journal
Journal of Medical Imaging and Radiation Sciences 50(2019)1, S38-S38
Synthese neuartiger Calixarenkäfige für die stabile Bindung von Ba2+ und Ra2+
Therapieansätze in der Nuklearmedizin mit Radium-223 beschränken sich zurzeit auf die Behandlung von Knochenmetastasen. Ziel ist es, das Anwendungsfeld für Radium-223 zu erweitern. Dafür werden Liganden entwickelt, die Radium-223 stabil binden und gleichzeitig eine spezifische Erkennungssequenz für diverse Krebsentitäten besitzen. Calixkronen mit funktionalisierten Seitenketten sind dafür vielversprechend.
Calixkrone-6-derivate mit Trifluormethylsulfonyl-  und 4-Nitrophenylsulfonyl-Seitenketten wurden synthetisiert und mittels NMR und UV/Vis auf ihre Komplexierungseigenschaften für Ba2+ untersucht. Anschließend wurden mittels eines Extraktionsassays Komplexierungen durchgeführt und die resultierenden Komplexe auf ihre Stabilität in Gegenwart anderer Ionen wie Ca2+ untersucht. Die Extraktionsversuche wurden im Chloroform/Wasser-Zweiphasensystem durchgeführt. Dabei wurde eine wässrige Metallsalzlösung ([133Ba]Ba2+ c.a. bzw. [224Ra]Ra2+ n.c.a.) definierter Konzentration vorgelegt und mit einer definierten Stoffmenge des jeweiligen Liganden in Chloroform für 1 h bei RT extrahiert.
Die beiden Calixarenderivate wurden in einer vierstufigen Synthese hergestellt. Anschließende Komplexierungsversuche mit Ba(ClO4)2 verliefen erfolgreich und die Komplexe wurden mittels NMR-Spektroskopie nachgewiesen. Für beide Liganden wurden Stabilitätskonstanten von 5,3-6,3 (Ba2+) bzw. 5,8 (Ra2+) berechnet. Die Radiumkomplexe beider Liganden waren gegenüber Ca2+-Ionen stabil (Release <5%), der Bariumkomplex des Nitrophenylsulfonylliganden war ebenfalls stabil (Release <5%), der des Trifluormethylsulfonylliganden zeigte 30% Release.
Die Wahl der sterisch anspruchsvollen und elektronenziehenden Sulfonylgruppen hatte positive Auswirkungen sowohl auf das Komplexierungsverhalten mit Ba2+ und Ra2+ als auch auf die Stabilität der resultierenden Komplexe in Gegenwart von zweiwertigen Fremdionen.
Keywords: Barium-133; Radium-224; Calixaren
57. Jahrestagung der DGN 2019, 03.-06.04.2019, Bremen, Deutschland
Abstract in refereed journal
Nuklearmedizin 58(2019), 136
- Secondary publication expected
Synthesis and Biological Investigation of A Novel Fluorine-18 Labeled Benzoimidazotriazine: A Potential Radioligand for In Vivo Phosphodiesterase 2A (PDE2A) PET imaging
Ritawidya, R.; Teodoro, R.; Wenzel, B.; Kranz, M.; Toussaint, M.; Dukic-Stefanovic, S.; Deuther-Conrad, W.; Scheunemann, M.; Brust, P.
Objectives: Cyclic nucleotide phosphodiesterase 2A (PDE2A), an enzyme which hydrolyzes the second messengers cAMP and cGMP, is highly enriched in distinct areas of the brain. Accordingly, PDE2A is involved in important signaling pathways related to normal brain function but also to
neurodegeneration and neuro-oncology . To enable the visualization of this protein in the brainwith PET, we developed a novel fluorine-18 radioligand for PDE2A.
Methods: Based on the benzoimidazotriazine (BIT) tricyclic scaffold, several fluorine-containing derivatives were synthesized via a multi-step synthesis route, and their inhibitory profiles were assessed by PDE isoenzyme-specific activity assays. The most potent and selective PDE2A ligand
BIT1 was radiolabeled via nucleophilic aromatic substitution of the corresponding 2-nitro pyridine precursor by [18F]fluoride in DMSO with thermal heating (Figure 1). [18F]BIT1 was isolated using semi-preparative HPLC (Reprosil-Pur C18-AQ column, 250 x 10 mm, 46% ACN/aqu. 20 mM
NH4OAc, flow 5.5 mL/min) followed by final purification with solid-phase extraction and formulation in isotonic saline containing 10% ethanol. Preliminary in vitro autoradiography and in vivo PET studies (60 min dynamic PET imaging, nanoScan® PET/MRI, MEDISO, Budapest, Hungary) of [18F]BIT1 were performed using pig brain slices and female CD-1 mice, respectively. The in vivo metabolism of [18F]BIT1 was investigated by radio-HPLC analysis of mouse plasma and brain samples at 30 min p.i.
Results: From the series of BIT derivatives, BIT1 was selected as candidate for PET imaging of PDE2A based on the most suitable inhibitory potential and profile (IC50 PDE2A3 = 3.3 nM;16-fold selectivity over PDE10A). [18F]BIT1 was successfully synthesized with a radiochemical yield of 54 ± 2% (n = 3, EOB), molar activities of 155 – 175 GBq/μmol (EOS) and radiochemical purities of ≥99%. [18F]BIT1 was stable in saline, pig plasma, and n-octanol up to 60 min at 37 °C. The distribution pattern of [ 18F]BIT1 in pig brain cryosections corresponds to the spatial distribution of PDE2A with accumulation in the striatal regions caudate nucleus and nucleus accumbens. Additionally, the displacement of [18F]BIT1 with BIT1 as well as TA1 (a potent PDE2A ligand) indicated saturability and selectivity of these binding sites. Uptake of [18F]BIT1 in the brain was shown by subsequent imaging studies in mice (SUVwhole brain = 0.7 at 5 min p.i.); however, more detailed analyses revealed nonspecific distribution of the tracer in the brain (78% parent compound at 30 min p.i.).
Conclusions: The potent and selective PDE2A inhibitor [18F]BIT1 binds in vitro in brain regions known to express PDE2A. Further structural modifications will be performed to develop radiotracers with improved brain uptake and target-selective accumulation in vivo.
1. Deutsche Forschungsgemeinschaft (German Research Foundation, SCHE 1825/3-1).
2. Scholarship Program for Research and Innovation in Science and Technology Project
(RISET-PRO)-Indonesia Ministry of Research, Technology and Higher Education (World
Bank Loan No: 8245-ID)
 S. Schröder, B. Wenzel, W. Deuther-Conrad, M. Scheunemann, P. Brust, Novel Radioligands
for Cyclic Nucleotide Phosphodiesterase Imaging with Positron Emission Tomography: An Update
on Developments Since 2012, Molecules 21 (2016) 650–685.
Keywords: Phosphodiesterases; positron emission tomography; molecular imaging; benzoimidazotriazines
International Symposium in Radiopharmaceutical Sciences, 26.-31.05.2019, Beijing, China
The effect of tumor volume changes on the boost-volume coverage in glioblastoma patients
Hessen, E.; Nijkamp, J.; Troost, E.; Makocki, S.; de Jong, M.; Dewit, L. H. G.; Jasperse, B.; van der Heide, U.; Borst, G.
Purpose/Objective: Radiotherapy is one of the main treatment modalities in the multimodal therapy of glioblastoma patients. The ongoing NRG-BN001 trial (NCT02179086) is evaluating whether boosting a sub-volume with photons or protons improves overall survival as compared to standard-dose photon irradiation. We hypothesize that anatomical changes during irradiation may affect the dose coverage and that these changes may have a greater impact on proton treatment plans compared to photon treatment plans.
Material & Methods: For 24 glioblastoma patients, the MRI was repeated half way during radiation treatment. Three patients had a gross total resection (GTR), four patients underwent a biopsy and 17 patients had a subtotal resection (STR). These patients were treated according to the EORTC-ACROP guideline. A simulated photon and proton treatment plan (intensity modulated proton therapy; IMPT) according to the NRG-BN001 trial were made retrospectively. In this trial, patients in the experimental arm receive a dose of 46Gy/30fr on the T2w/FLAIR abnormalities and 75Gy/30fr on the planning target boost volume (PTV-7500). The PTV-7500 was defined as the resection cavity and/or contrast enhancing lesion on the T1w post gadolinium sequence of the MRI plus a margin of 5 mm (CTV) plus a 4 mm expansion in all dimensions. The trial constraints states that at least 95% of the PTV-7500 should receive 75Gy. To analyze the effect of anatomical changes during treatment on the dose coverage, we evaluated the planned dose distribution (based on the planning MRI) on the delineated PTV-7500 of the repeated MRI.
Results: The median time interval between the two MRIs was 25.5 days (range 15 – 36 days). Between the two scans, the PTV-7500 volume changed with a median of -0.1cc. However, we observed a wide range of -52.8 to +52.2cc. For the photon treatment plans we observed that 83% (n=20) of the patients showed a decline in PTV-7500 coverage (corresponding with a median decline of 6.5% and 8.3cc). The quartile of patients (n=6) with the largest PTV-7500 increase showed a 10% reduction in dose coverage (corresponding with a median volume of 33.2cc). There was no significant difference in coverage changes of the boost volume between the GTR, biopsy only and STR patients (p=0.632). The evaluation of the IMPT plans is ongoing and will be presented during the conference.
Conclusion: During fractionated radiation treatment for glioblastoma patients we observed large target volumetric changes in the boost volume half way during treatment. These target volume changes may lead to substantial declines in dose coverage when patients are treated according to dose-escalation protocol boosting specific sub-volumes. Thus, an important subset of glioblastoma patients may benefit from an MRI guided dose escalation strategy.
ASTRO, 15.-18.09.2019, Chicago, USA
Abstract in refereed journal
International Journal of Radiation Oncology Biology Physics 105(2019)1, E99-E100
Robust optimization of dose-volume metrics for prostate HDR-brachytherapy incorporating target and oar volume delineation uncertainties
Balvert, M.; Den Hertog, D.; Hoffmann, A. L.
In radiation therapy planning, uncertainties in the definition of the target volume yield a risk of underdosing the tumor. The traditional corrective action in the context of external beam radiotherapy (EBRT) expands the clinical target volume (CTV) with an isotropic margin to obtain the planning target volume (PTV). However, the EBRT-based PTV concept is not directly applicable to brachytherapy (BT) since it can lead to undesirable dose escalation. Here, we present a treatment plan optimization model that uses worst-case robust optimization to account for delineation uncertainties in interstitial high-dose-rate BT of the prostate. A scenario-based method was developed that handles uncertainties in index sets. Heuristics were included to reduce the calculation times to acceptable proportions. The approach was extended to account for delineation uncertainties of an organ at risk (OAR) as well. The method was applied on data from prostate cancer patients and evaluated in terms of commonly used dosimetric performance criteria for the CTV and relevant OARs. The robust optimization approach was compared against the classical PTV margin concept and against a scenario-based CTV margin approach. The results show that the scenario-based margin and the robust optimization method are capable of reducing the risk of underdosage to the tumor. As expected, the scenario-based CTV margin approach leads to dose escalation within the target, whereas this can be prevented with the robust model. For cases where rectum sparing was a binding restriction, including uncertainties in rectum delineation in the planning model led to a reduced risk of a rectum overdose, and in some cases, to reduced target coverage.© 2019 INFORMS
Keywords: Brachytherapy; Delineation uncertainties; Mixed-integer linear optimization; Robust optimization; Treatment planning
INFORMS Journal on Computing 31(2019)1
Solving the Kuramoto Oscillator Model on Random Graphs
The problem of synchronization is recently attracting much attention because it relates to current topics in science. The dynamics of electrical grids can be affected by de-synchronizations between supplier and consumer nodes. In brains, synchronization of neuronal activity plays an important role in most functions. The Kuramoto model describes systems of coupled oscillators which, which exhibit non-trivial behavior on complex graphs, making it a suitable tool to study the synchronization dynamics of brains an other systems.
Numerical solution of Kuramoto type ordinary differential equations for long times and large systems requires strong computation power, due to the inherent chaoticity of this nonlinear system.
This poster presents a GPU implementation of a solver achieving large speedups over CPU on sparse random graphs. The key to performance here, is the presented memory layout which supplements the SIMT usage of our design.
# extended abstract
The problem of synchronization is recently attracting much attention because it relates to current topics in science. The dynamics of electrical grids can be affected by de-synchronizations between supplier and consumer nodes. In brains, synchronization of neuronal activity plays an important role in most functions.
Using the Kuramoto model, we are studying a range of problems, from basinc questions about synnchronisation transitions on disordered lattices and random graphs to problems mentioned in the short abstract. The model shows komplex behavior on human connectome graph, which allow the study of synchronization in the human brain. An extension of the model allows modeling power grid networks[3,4].
Very intensive Simulations are required to obtain precise result especiall near criticality, which these systems show at synchronization transitons. To enable the study of these systems at sufficent precision, we implemented a GPU code, which we are presenting in this poster. To this end we used boost::odeint to get the standart numerical integartion out of the way an focus on the most performance critical aspect: the evaluation of the model itself. The key to our implementation is the choice of SIMT vectorization and a suitable memory layout, which are presented in the poster. The aspects also remain the same, when we add the extension to the second-order Kuramoto Model, which is required to model powergrids.
 Kuramoto, Y. In Araki, H. (ed.) Mathematical Problems in Theoretical Physics, vol. 39 of Lecture Notes in Physics, Berlin, 420
 Villegas, P., Moretti, P. & Muñoz, M. A. Scientific Reports 4, 5990 (2014).
 Filatrella, G., Nielsen, A. H. & Pedersen, N. F. Eur. Phys. J. B 61, 485–491 (2008)
 Ódor, G. & Hartmann, B. Phys. Rev. E 98, 022305 (2018).
Keywords: GPGPU; random graph; Kuramoto model
GTC 2019 Silicon Valley, 17.-21.03.2019, San Jose, CA, USA
Contribution to WWW
Invited lecture (Conferences)
GPU Day 2019, 11.-12.07.2019, Budapest, Hungary
GTC China, 16.-19.12.2019, Suzhou, China
Beneficiation of parisite-rich rare earth ore from the Nam Xe South deposit, Vietnam
Möckel, R.; Heinig, T.; Cardenas Vera, A. F.; Gutzmer, J.; Merker, G.; van Phan Quang, .
Parisite-rich rare earth element (REE) ores from the Nam Xe deposit in northern Vietnam were beneficiated on a lab scale. Beneficiation experiments included, amongst others, sensor-based sorting, magnetic separation and flotation. Particular analytical focus during all experiments was set on the grain size, association and intergrowth of of the main REE carrier mineral parisite, which is finely intergrown with minerals of the barite-celestine solid solution series. All experiments were accompanied by mineral liberation analysis and chemical assays in order to be able to provide direction towards an optimal beneficiation strategy for this REE ore with its rather unique mineralogy. Special focus was set on the grain characteristics of the main REE carrier mineral parisite, which is finely intergrown above all with minerals from the barite-celestine solid solution series.
A multi-stage flotation technique was developed that uses an ambient rougher and a hot cleaner stage. Concentrates with 40% TREO grade with a total recovery of about 80% were achieved. It was shown that a combination with a sensor-based pre-sorting prior to the flotation can increase the input grade for flotation considerably by a nearly loss-free rejecting of virtually barren bed rock. The process combination developed holds good potential for further improvements.
15th Biennial Meeting of the Society for Geology Applied to Mineral Deposits, 27.-30.08.2019, Glasgow, Scotland
Fragment molecular orbital (FMO) method for studying actinide/lanthanide interaction with DNA/protein
Tsushima, S.; Mochizuki, Y.; Fahmy, K.
Due to its potential health and environmental impacts, actinide binding to biomolecules has been a subject of intensive investigations. A large number of experimental works have been carried out but our understanding remains mostly in a macroscopic scale. Modeling actinide interaction with large biomolecules using ab initio quantum chemical calculations may drastically expand our molecular level knowledge but is challenged by a demand for huge computational resources.
Our strategy to overcome this difficulty is to apply fragment molecular orbital (FMO) method. In FMO, the molecular system of interest is partitioned into small fragments. Each fragment and fragment pair is subject to self-consistent field calculations under environmental electrostatic potentials and the electronic structure of the whole system is reconstituted . This procedure drastically reduces computational cost of Hartree Fock calculations from N3 to N2 (or less) and is readily parallelizable. FMO has been extended to MP2 and to DFT to include electron correlation and was successfully applied to the systems such as hydrated DNA .
Currently we are upgrading the FMO program Abinit-MP  to implement 5f elements into the program. We first choose uranyl-bound DNA for a case study. Calculations are performed as follows. UO22+-bound d(CGCGAATTCGCG)2 (Dickerson-Drew dodecamer) with 20 Na+ ions and SPC/E water shell with 10 Å thickness is first thermally equilibrated and subsequently submitted to MD simulation at 300 K for 100 ns interval using AMBER 14 program. Force field parameters for UO22+ and coordinating water are those developed by Pomogaev et al. . At each 1 ns time step of MD simulation, the structure is extracted and submitted to FMO single point energy calculation at the MP2 level. In FMO, nucleic unit is appropriately divided into sugar, base, and phosphate fragments. Inter-fragment interaction energy analysis is performed to explore the binding affinity of uranyl to DNA and its influence on base pairing.
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Joint 12th EBSA and 10th ICBP-IUPAP Biophysics Congress, 20.-24.07.2019, Madrid, Spain
Observations of Coherent Optical Transition Radiation Interference Fringes Generated by Laser Plasma Accelerator Electron Beamlets
We report initial observations of coherent optical transition radiation interferometry (COTRI) patterns generated by microbunched electrons from laser-driven plasma accelerators (LPAs). These are revealed in the angular distribution patterns obtained by a CCD camera with the optics focused at infinity, or the far-field, viewing a Wartski two-foil interferometer. The beam divergences deduced by comparison to results from an analytical model are sub-mrad, and they are smaller than the ensemble vertical beam divergences measured at the downstream screen of the electron spectrometer. The transverse sizes of the beamlet images were obtained with focus at the object, or near field, and were in the few-micron regime as reported by LaBerge et al. . The enhancements in intensity are significant relative to incoherent optical transition radiation (OTR) enabling multiple cameras to view each shot. We present two-foil interferometry effects coherently enhanced in both the 100-TW LPA at 215 MeV energy at Helmholtz-Zentrum Dresden-Rossendorf and the PW LPA at 1.0-GeV energy at the University of Texas-Austin. A transverse emittance estimate is reported for a microbunched beamlet example generated within the plasma bubble.
Keywords: LPA; microbunching; COTR; beam size; divergence
Contribution to proceedings
18th Advanced Accelerator Concepts Workshop (AAC 2018), 12.-17.08.2018, Breckenridge, CO, USA
2018 IEEE Advanced Accelerator Concepts Workshop (AAC): IEEE, 978-1-5386-7721-6
Bacillus safensis JG-B5T affects the fate of selenium by extracellular production of colloidally less stable nanoparticles
Fischer, S.; Krause, T.; Lederer, F.; Merroun, M. L.; Shevchenko, A.; Hübner, R.; Stumpf, T.; Jordan, N.; Jain, R.
Bacteria strain Bacillus safensis JG-B5T is an obligate aerobic microorganism isolated from uranium mining waste pile. The role played by this microorganism in the transport of selenium is poorly understood. This study demonstrated that B. safensis JG-B5T can reduce 70 % of 2.5 mM selenite whereas selenate reduction was not observed. Formation of the resulting biogenic elemental selenium nanoparticles (BioSeNPs) occurred exclusively extracellularly. The ζ-potential of the produced BioSeNPs varied from −44.2 (±0.2) mV to −10.6 (±3.3) mV when Na+:Se ratio was varied from 0 to 0.8 (mM:mM), suggesting a lower colloidal stability. Further experiments in two-chamber reactors and transmission electron microscopy revealed that direct cell contact is essential for selenite reduction by B. safensis JG-B5T. The selenite reduction is likely primarily mediated through membrane-associated proteins, like succinate dehydrogenase as revealed by genome and proteomics analysis. Altogether, this study showed that aerobic bacteria B. safensis JG-B5T is involved in decreasing the environmental bioavailability and toxicity of selenium by membrane protein-mediated reduction of selenite oxyanions and formation of extracellular BioSeNPs with low colloidal stability.
Keywords: Obligate aerobic; two-chamber reactor; proteomics; membrane-associated proteins; selenite
Journal of Hazardous Materials 384(2020), 121146
Photocatalytic Oxygenation of Cyclohexene Initiated by Excitation of [UO2(OPCyPh2)4]2+ under Visible Light
Oxygenation reaction of cyclohexene was studied under presence of a 4-fold UO22+ complex with cyclohexyldiphenylphosphine oxide, [UO2(OPCyPh2)4]2+, and blue light irradiation at 436 nm in acetonitrile. As a result, 1,6-hexanedial, cyclohexene oxide, 2-cyclohexen-1-one, and 2-cyclohexen-1-ol were photocatalytically generated as oxygenated products with TOF = 6.7 h−1. In contrast, dimerization of cyclohexene was observed under Ar atmosphere. This implies that a hydrogen atom at the allyl position is abstracted by photoexcited *[UO2(OPCyPh2)4]2+ to give a cyclohexene radical and a U(V) intermediate [UVO2(OPCyPh3)4]+, being well supported by DFT calculation. Under O2 atmosphere, the former reacts with dissolved O2 to give 2-cyclohexen-1-one and 2-cyclohexen-1-ol. Dissolved O2 would be activated by the U(V) intermediate to afford O22− in the end, which drives oxygenation of C=C bond of unreacted cyclohexene.
ACS Omega 4(2019)4, 7194-7199
Sensitivity and uncertainty analysis for geochemical models for repository safety assessment
Stockmann, M.; Becker, D.-A.; Noseck, U.; Brendler, V.
A key component of safety assessment for radioactive waste repositories in deep geological formations is the simulation of potential radionuclide release scenarios and the transport of radionuclides through the repository system. The realistic modelling of (hydro-)geochemical processes is of high relevance for assessing the migration of radionuclides in groundwater systems. One important retardation process for radionuclides to be considered is sorption onto mineral surfaces of the host rock / sediments. Due to the heterogeneities of the natural system and the high complexity of the geochemical models with uncertain or varying input parameters, it is important to understand which of the input parameter uncertainties have considerable influences on the model output uncertainty. This in turn allows model reduction required to upscale from the molecular to the plug scale. Consequently, we performed sensitivity and uncertainty analysis (SA/UA) to investigate and understand our geochemical model.
For the quantification of the contaminant retention in groundwater, the solid/liquid distribution coefficients (Kd-values) calculated for a given groundwater/rock system are traditionally used. Most often conventional concepts with constant Kd values are applied in reactive transport simulations. Such an approach has the advantage to be simple and computationally fast but cannot reflect changes in geochemical conditions that will occur during the evolution of the repository system, e.g. due to climatic changes. Due to the German safety criteria with an assessment period of about 1 million years it is necessary to consider the impact of such geochemical changes on the radionuclide transport and retardation. For this, we developed a new approach, where the smart Kd concept (www.smartkd-concept.de)  is modified in complex geochemical models including mechanistic sorption models, and implemented it in reactive transport calculations [2, 3]. Possible migration scenarios for repository-relevant radionuclides (isotopes of Am, Cm, Cs, Ni, Np, Pu, Ra, Se, Th and U) through a typical sedimentary rock system covering potential repository host rocks, namely salt and clay formations in Northern Germany as natural geological barrier, were developed in the first stage.
Smart Kd-values and their associated sensitivities and uncertainties were computed for a wide range of important geochemical input parameters / boundary conditions such as pH value, ionic strength, concentration of competing cations and complexing ligands, e.g. dissolved inorganic carbon (DIC) and calcium (Ca2+). Our toolbox coupled the geochemical speciation code PHREEQC  with the numeric tool UCODE  and SimLab2.2/4 . SimLab has the advantage to permit a simultaneous variation of all input parameters according to their probability density functions and mutual correlations. It provides (in contrast to UCODE, which also incorporates some simple SA/UA algorithms) methods for Global SA. Comparable SA/UA have been done with a new software package RepoSUN, which is based on SimLab4 . For the varying parameters uncertainty intervals were defined from field investigations and log-uniform distributions were assumed for all parameters, except for the pH value, which was assumed to be uniformly distributed. The results, i. e. the smart Kd values, were analyzed in the following way:
o As the output distribution covers several orders of magnitude, a log-transformation was performed on the output data. Then the computed a-priory multidimensional smart Kd matrices (see for U(VI) in Fig. 1, left) are accessible for interpolations during subsequent transport simulations.
o A histogram of the model output visualizes the distribution (see for U(VI) in Fig. 1, right).
o Some statistical measures were calculated to characterize the distribution (minimum, maximum, mean, standard deviation).
o Sensitivity measures were calculated for each of the input parameters: the standardized regression coefficient (SRC), the standardized rank regression coefficient (SRRC) and the variance-based first-order sensitivity index (SI1).
On the basis of the results it could be shown that the smart Kd approach goes considerably beyond the conventional concepts. We could illustrate that constant Kd values (see for U(VI) in Fig. 1, right, green line) used in previous transport simulations  are a crude assumption, as in reality they rather range over several orders of magnitude. Moreover, with the results from the SA, the most important input parameters influencing the radionuclide retardation can be identified (key parameters of the model). The calculated sensitivity indices allowed us to assess the most and less sensitive parameters. From the visualized smart Kd matrix for U(VI) (Fig. 1, left) it is obvious that mainly the pH value and the DIC influences the sorption of U(VI) under the given conditions. SA is a useful means for reducing the complexity of a geochemical model by focusing on the most important input parameters.
Ninth International Conference on Sensitivity Analysis of Model Output (SAMO'19), 28.-30.10.2019, Barcelona, Spain
Time efficient scatter correction for time-of-flight PET: the immediate scatter approximation
Utilization of Time-Of-Flight (TOF) information allows to improve image quality and convergence rate in iterative PET image reconstruction. In order to obtain quantitatively correct images accurate scatter correction (SC) is required that accounts for the non-uniform distribution of scatter events over the TOF bins. However, existing simplified TOF-SC algorithms frequently exhibit limited accuracy while the currently accepted gold standard — the TOF extension of the single scatter simulation approach (TOF-SSS) — is computationally demanding and can substantially slow down the reconstruction. In this paper we propose and evaluate a new accelerated TOF-SC algorithm in order to improve this situation. The key idea of the algorithm is the use of an immediate scatter approximation (ISA) for scatter time distribution calculation which speeds up estimation of the required TOF scatter by a factor of up to five in comparison to TOF-SSS. The proposed approach was evaluated in dedicated phantom measurements providing challenging high activity contrast conditions as well as in representative clinical patient data sets. Our results show that ISA is a viable alternative to TOF-SSS. The reconstructed images are in excellent quantitative agreement with those obtained with TOF-SSS while overall reconstruction time can be reduced by a factor of two in whole-body studies, even when using a listmode reconstruction not optimized for speed.
Keywords: PET; Scatter Correction; Immediate Scatter Approximation; Image Reconstruction; TOF; SSS; TOF-SSS; TOF-SC; ISA
Physics in Medicine and Biology 64(2019), 075005
Towards best practice guidelines for Euler-Euler simulations of poly-disperse bubbly flows
Lucas, D.; Liao, Y.; Rzehak, R.; Krepper, E.
Poly-disperse bubbly flows are involved in normal operation as well as in accident scenarios of Light Water Reactors. There are many activities to qualify CFD-methods for the simulation of safety-relevant processes. However, due to the complexity of such flows many details have to be carefully considered to define a proper setup for such simulations. The present paper aims at the establishment of a guideline how to prepare and conduct such a simulation as well as to evaluate the simulation results according to the best practice. The procedure has to start with an analysis of the expected flow situation, flow parameters and observed phenomena. Accordingly a classification should be done. Beside boundary conditions, the numerical grid, the time stepping and other issues a careful selection of the modelling framework (e.g. inclusion of a population balance, two- or multi-field approach) and the closure models has to be done based on the previous analysis. A set of well suited closure models is defined by the so-called baseline model for poly-disperse flows. Numerical convergence has to be checked throughout the simulation. For the comparison with experimental data possible uncertainties of the input data used and the experimental data used for comparison have to be considered. Besides the presentation of the state of the art best practice guidelines also their limitation and requirements for future research are discussed.
Keywords: CFD; bubbly flow; Euler-Euler; best practice guidelines
Contribution to proceedings
The 18th International Topical Meeting on Nuclear Reactor Thermal Hydraulics (NURETH-18), 18.-22.08.2019, Portland, OR, USA
The 18th International Topical Meeting on Nuclear Reactor Thermal Hydraulics (NURETH-18), 18.-22.08.2019, Portland, OR, USA
Influence of the bubble size distribution on the bubble column flow regime
Lucas, D.; Ziegenhein, T.
The role of the bubble size dependent lateral lift force on the flow regime is experimentally investigated in a tall bubble column. In the experiments, only the initial bubble size distribution was modified by using a gas sparger with different injection needles and varying the flow through specific injection needles. The gas flow rate was kept unchanged in all experiments. Depending on the bubble size distribution homogeneous, transitional or heterogeneous flow regimes were observed. The flow regime is in good agreement with the predictions from the stability criterion obtained by a previously done linear stability analysis for poly-dispersed flow. It was found that as a rule of thumb the following criterion can be used.
If most of the gas volume is transported by bubbles smaller than the critical diameter at which the lift force changes its sign, the flow is stabilized leading to a homogeneous flow regime. If most of the gas volume is transported by bubbles larger than that diameter the flow is de-stabilized leading a heterogeneous flow regime. If the fraction of gas transported by small and large bubbles is about the same, the initial conditions remain dominant throughout the column height.
Keywords: bubble size; lift force; stability; bubble column; flow regime; regime transition
International Journal of Multiphase Flow 120(2019), 103092
- Secondary publication expected from 12.08.2020
Quantum Critical Dynamics of a Heisenberg-Ising Chain in a Longitudinal Field: Many-Body Strings versus Fractional Excitations
Wang, Z.; Schmidt, M.; Loidl, A.; Wu, J.; Zou, H.; Yang, W.; Dong, C.; Kohama, Y.; Kindo, K.; Gorbunov, D. I.; Niesen, S.; Breunig, O.; Engelmayer, J.; Lorenz, T.
We report a high-resolution terahertz spectroscopic study of quantum spin dynamics in the antiferromagnetic Heisenberg-Ising spin-chain compound BaCo2V2O8 as a function of temperature and longitudinal magnetic field. Confined spinon excitations are observed in an antiferromagnetic phase below TN ≃ 5.5 K. In a field-induced gapless phase above Bc = 3.8 T, we identify many-body string excitations as well as low-energy fractional psinon/antipsinon excitations by comparing to Bethe-Ansatz calculations. In the vicinity of Bc, the high-energy string excitations are found to be dynamically dominant over the fractional excitations.
Physical Review Letters 123(2019), 067202
Protecting Pulsed High-Power Lasers with Real-Time Object Detection
Kelling, J.; Gebhardt, R.; Helbig, U.; Bock, S.; Schramm, U.; Juckeland, G.
In Petawatt laser systems, firing at 10Hz, suddenly appearing scatterers can damage components. Damage(-spreading) can be avoided by suspending operation immediately on occurrence of such an event. This poster presents our approach for the automatic detection of critical failure states in real-time, employing state-of-the-art object localization on intensity profiles of the laser beam.
Learn, how we fitted the You Look Only Once (YOLO) approach, which is suited to low-latency object detection, to our problem and how we adapted the required multi-step training protocol to the available experimental data.
In this application accuracy trumps high recall, as false positives would severely impede productivity or even render our system useless. This had us refrain from general anomaly detection and thus we also present different ways in which we tune the object-detection for minimal false-positive rates.
# extended abstract
High-power lasers are operated at our research center for investigations of exotic states of matter and medical applications, among others. This project to improve the automatic shutdown/interlock system of two lasers (one in operation, one currently under construction) has the goal of reducing the probability of, potentially expensive, damage-spreading scenarios, while at the same time avoiding false alarms. In order to achieve high precision, we train for high recall only for known indicators, instead of using anomaly detection.
After we presented a proof-of-concept for this type of failure-state-detection at GTC 2018, where the main challenge was in dealing with a far too small dataset, we are now working on a pure deep-learning approach driven by systematic experimental data. In the new design, intended for production use, the classification takes place on differences between a running average of non-signaling images and the current shot. This is required, because no images can be obtained which can be classified as "good" without context. In order to achieve fast object-detection, to highlight potential problems for the operator, the you look only once (YOLO) approach, which we modify by removing the final layers for bounding-box prediction and train the network to directly produce an expressive feature map (lazy YOLO).
From this talk, the audience can learn how we adapted the well-known YOLO approach to our real-world application, from the employed network to the multi-step training protocol. Another topic is the design for short response times, to which end we employ Caffe, OpenCV on GPU and use C++ as main programming language instead of python.
 Redmon, J., Farhadi, A.: YOLO9000: Better, Faster, Stronger, ArXiv e-prints, 2016
Keywords: Image Classification; Caffe; automatic Laser-safety shutdown; Object Detection
GTC 2019 Silicon Valley, 17.-21.03.2019, San Jose, CA, USA
Contribution to WWW
Dimeric Uranium(VI)–Citrate Complexes: Structures and Dynamics
The aqueous chemistry of the uranium(VI)–citrate system is challenging, as evidenced by still controversial discussions on complex stoichiometries and structures [1–4]. For a sound understanding of the chemical behavior in general and the environmental fate in particular, knowledge of both aqueous speciation and molecular structures in solution is crucial. Here, complexes formed by the uranyl ion, U(VI), and citrate (Cit) were examined in the pH range 2–8 by combining one- and two-dimensional NMR with UV-Vis, ATR FT-IR, and EXAFS spectroscopies as well as DFT-based quantum chemical calculations.
Upon complexation, a chiral center is induced in Cit’s central carbon, resulting in the formation of two diastereomeric pairs of enantiomers, whereupon the dimeric complexes exhibit syn and anti configured isomers. In fact, the combination of 17O NMR (note: at natural abundance) and DFT calculations allowed an unambiguous decision on complex geometry and overall configurations. It is evidenced for the first time that the syn isomer is favored in aqueous solution in contrast to the preferably crystallizing anti isomer. Both isomers coexist and interconvert among one another, with a rate estimated to be in the order of 10² s–¹ at 25 °C in acidic media, and a corresponding activation energy of approximately 60 kJ mol–¹.
Upon increasing pH, the ternary dimeric U(VI)–Cit mono- and bis-hydroxo (2:2:1 and 2:2:2) complexes form as evidenced by both UV-Vis and ATR FT-IR spectroscopy. The latter methods provided stability constants (log β): 19.5 (2:2:0), 14.0 (2:2:1), and 6.5 (2:2:2). Accordingly, the process can be referred to as U(VI) hydrolysis within the U(VI)–Cit complex as the two coordinating water molecules in the respective fifth coordination site each abstract H+. Thus, any U(VI)-coordinating water in ever so stable complexes is susceptible to hydrolysis even in strong acidic media as consequence of the interplay between metal ion Lewis acidity and solution pH.
Virtually all single-crystal X-ray structures containing the dimeric U(VI)–Cit complex in any manner, reveal anti configuration, e.g. . The predominance of the syn isomer in solution was hitherto unnoticed, demonstrating that, particularly upon different physico-chemical properties of the isomers, the (crystalline) solid phase does not necessarily reflect speciation and structures found in (aqueous) solution, underlining the importance of rigorous solution studies.
 I. Feldman et al., J. Am. Chem. Soc., 1954, 76, 4726.
 M. T. Nunes and V. M. S. Gil, Inorg. Chim. Acta, 1987, 129, 283.
 S. P. Pasilis and J. E. Pemberton, Inorg. Chem., 2003, 42, 6793.
 M. Basile et al., Chem. Commun. 2015, 51, 5306.
Keywords: uranium; uranyl; U(VI); citric acid; molecular structure; NMR; ATR FT-IR; UV-Vis; spectroscopy; ternary complex; uranium hydrolysis; stability constant; isomerization
Jahrestagung der Fachgruppe Nuklearchemie 2019, 25.-27.09.2019, Dresden, Deutschland
Simultaneous 8.2 keV phase-contrastimaging and 24.6 keV X-ray diffraction fromshock-compressed matter at the LCLS
Seiboth, F.; Fletcher, L. B.; Mcgonegle, D.; Anzellini, S.; Dresselhaus-Cooper, L. E.; Frost, M.; Galtier, E.; Goede, S.; Harmand, M.; Lee, H. J.; Levitan, A. L.; Miyanishi, K.; Nagler, B.; Nam, I.; Ozaki, N.; Rödel, M.; Schropp, A.; Spindloe, C.; Sun, P.; Wark, J. S.; Hastings, J.; Glenzer, S. H.; Mcbride, E. E.
In this work, we demonstrate simultaneous phase-contrast imaging (PCI) and X-ray diffractionfrom shock compressed matter at the Matter in Extreme Conditions endstation, at the LinacCoherent Light Source (LCLS). We utilize the chromaticity from compound refractive X-ray lensesto focus the 24.6 keV 3rd order undulator harmonic of the LCLS to a spot size of 5lm on target toperform X-ray diffraction. Simultaneous PCI from the 8.2 keV fundamental X-ray beam is used tovisualize and measure the transient properties of the shock wave over a 500lm field of view.Furthermore, we demonstrate the ability to extend the reciprocal space measurements by 5 Angstroem, rel-ative to the fundamental X-ray energy, by utilizing X-ray diffraction from the 3rd harmonic of theLCLS.
Keywords: Phase Contrast Imaging; PCI; Matter in Extreme Conditions; MEC; LCLS; shock compression; x-ray diffraction; XFEL; germanium; shock; release
Applied Physics Letters 112(2018)22, 221907
A Polka-Dot Pattern Emerges in Superfluid Helium
A surprising two-dimensional pattern appears in superfluid helium-3 when the liquid is confined to a micrometer-thick cell and exposed to a magnetic field.
Physics 12(2019), 20
Low anisotropic upper critical fields in SmO1−xFxFeAs thin films with a layered hybrid structure
Haindl, S.; Kampert, E.; Sasase, M.; Hiramatsu, H.; Hosono, H.
We report on the upper critical fields in SmO1−xFxFeAs thin films prepared by pulsed laser deposition. With an F-content gradient along their thickness, the films could be described approximately as layered two-phase hybrid structures comprised of one superconducting layer and one antiferromagnetic layer. An analytical characterization of different thin film samples by Auger electron spectroscopy and energy-dispersive x-ray spectroscopy in scanning transmission electron microscopy is provided and structural defects, such as antiphase boundaries, were confirmed for films grown at lower deposition temperatures. Electrical transport measurements in pulsed magnetic fields yielded upper critical fields higher than 80 T with an anisotropy γHc2 ≤ 2.25.
Superconductor Science and Technology 32(2019), 044003
Microscopic and spectroscopic investigations of the interactions of a Halobacterium-isolate with uranium
Hilpmann, S.; Bader, M.; Bachran, M.; Steudtner, R.; Schmidt, M.; Stumpf, T.; Cherkouk, A.
Rock salt formations are potential host rocks for the long-term storage of high-level radioactive waste in a deep geological repository, besides clay and crystalline rock. There are multiple studies about the geological, geochemical and geophysical properties of these host rocks. However, there exists still a lack of knowledge about indigenous microorganisms and their influence on the chemical speciation. For a long-term risk assessment, it is of high interest to study how these microorganisms interact with radionuclides. Therefore, the interactions of an extremely halophilic archaeon, Halobacterium sp. GP5 1-1 with uranium, one of the major radionuclides of concern, were investigated in detail. This extremely halophilic archaeon was isolated from a German rock salt sample. Different microscopic and spectroscopic methods were combined to decipher the occurring processes on a molecular level.
To investigate the interaction kinetics of uranium(VI) onto the cells of Halobacterium sp. GP5 1-1, time-dependent association experiments with two different uranium(VI) concentrations were performed. At both concentrations the amount of bioassociated uranium(VI) increased with the incubation time. It was determined that the association process at the higher concentration (30 µM) was much slower than the kinetic at the lower uranium(VI) concentration (10 µM).
Various microscopic and spectroscopic methods were used to understand the interaction mechanisms on a molecular level. Overall, the association process is not exclusively a biosorption, which is a passive process and in general completed after a short time of incubation (0 – 2 h) . The microscopic images of the live/dead staining show the formation of cell agglomerates after a certain exposition time at both concentrations. During the process, organic matter is excreted from the cells. Therefore, more functional groups are available for further uranium(VI) binding.
Electron microscopic images of the cells allowed drawing conclusions about different microbe-radionuclide interactions at different uranium(VI) concentrations. A biomineralization takes place at lower concentrations (10 µM) and uranium(VI) is bound to biofilm-like structures at higher concentrations (60 µM).
Using time-resolved laser-induced luminescence spectroscopy, different aqueous species could be extracted from the supernatant. These species differ slightly in dependence on the uranium(VI) concentration. In both cases, a uranyl-carbonate-complex is formed during the association process due to microbial released CO2. Additionally the formation of a phosphate species in the cell pellets at low uranium(VI) concentrations was observed in a uranium(VI) concentration-dependent experiment (10-60 µM). In contrast, at higher uranium(VI) concentrations a carboxylic species was formed. This is in agreement with the already mentioned excretion of organic matter from the cells during the uranium(VI) incubation.
These findings offer new insights into the microbe-actinide interactions at highly saline conditions relevant to high-level radioactive waste disposal in rock salt.
 J. R. Lloyd, L. E. Macaskie (2002) in “Interactions of Microorganisms with Radionuclides” (Eds.: M.J. Keith-Roach, F. R. Livens), Elsevier, pp. 313-381
Migration 2019, 15.-20.09.2019, Kyoto, Japan
Complex formation between UO22+ and α-isosaccharinic acid: insights on a molecular level
Cellulosic materials present as tissue, paper, wood, or filter materials in low and intermediate level waste will degrade under alkaline conditions if water ingresses in a cementitious backfilled repository. The main degradation product is isosaccharinic acid. Complex formation with isosaccharinic acid may adversely affect the retention of radionuclides by sorption or formation of solid phases. Hence, this compound is of particular concern in the context of nuclear waste disposal. Structural information of complexes are limited to spherical metal centers and little is known about the interaction of uranyl (UVIO22+) with isosaccharinic acid. Therefore, the interaction of UO22+ with α-isosaccharinate (ISA) was studied under acidic conditions focusing particularly on the structural characterization of the formed complexes. Attenuated total reflection Fourier-transform infrared (ATR-FTIR), nuclear magnetic resonance (NMR), UV-Vis, extended X-ray absorption fine structure (EXAFS) spectroscopy and electrospray-ionization mass spectrometry (ESI-MS) were combined with theoretical calculations to obtain a process understanding on the molecular level. The dominant binding motifs in the formed complexes are 5- and 6-membered rings involving the carboxylic group as well as the α- or β-hydroxy group of ISA. Two concentration dependent complex formation mechanisms were identified involving either mono- ([UO2(ISA)(H2O)3]+) or binuclear ([(UO2)2(ISA)(H2O)6]3+) species. Furthermore, this study unveils the interaction of UO22+ with the protonated α-isosaccharinic acid (HISA) promoting its transformation to the corresponding α-isosaccharinate-1,4-lactone (ISL) and inhibiting the formation of polynuclear UO22+-ISA species. Future studies on related systems will benefit from the comprehensive knowledge concerning the behavior of ISA as complexing agent gained in the present study.
Keywords: Uranium; Isosaccharinic acid; Complexation; Lactonization; Spectroscopy
Dalton Transactions 48(2019), 13440-13457
From Exploration towards Predictive Geometallurgy - The Role of SEM-based Automated Mineralogy and Statistical Assessment
Birtel, S.; Bachmann, K.; Büttner, P.; Tolosana Degado, R.; van den Boogaart, K. G.; Gutzmer, J.
Geometallurgical models are constructed to quantitatively predict how ores will behave during extraction and beneficiation. Depending on data availability, complexity of data and operational stage different classes of geometallurgical models can be distinguished: 1) resource potential, 2) recoverable resources, 3) first order predictive models, 4) predictive models, and 5) real-time mining models. Here, two case studies are presented where modal mineralogy and microstructural data obtained from SEM-based image analysis are combined with complementary analytical data and statistically assessed in order to predict raw material behaviour during mineral processing. For both case studies, the necessary steps to develop existing models into truly predictive geometallurgical models are outlined. The first case study concerns the recovery of Sn from a historic flotation tailings storage facility. The second case study centres on the recovery of PGE as by-products from a chromite ore deposit as a first order predictive geometallurgical model.
Keywords: SEM based automated mineraloy; statistcal assement; case studies; process optimization
Contribution to proceedings
15th Biennial Meeting of the Society for Geology Applied to Mineral Deposits, 27.-30.08.2019, Glasgow, UK
Proceedings to 15th Biennial Meeting of the Society for Geology Applied to Mineral Deposits, 1474-1477
15th Biennial Meeting of the Society for Geology Applied to Mineral Deposits, 27.-30.08.2019, Glasgow, UK
Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties
O'Toole, N.; Lecourt, C.; Suffren, Y.; Hauser, A.; Khrouz, L.; Jeanneau, E.; Brioude, A.; Luneau, D.; Desroches, C.
The photophysical properties of the compound [(ThiaSO₂)(MnII)₂(DMF)₄(H₂O)₂] (2), ThiaSO₂ = p-tert-butylsulfonylcalixarene, are presented and compared to the ones of [(ThiaSO₂)₂(MnII)₄F]K (1). The orange luminescence of 2 is attributed, as for 1, to the MnII centred ⁴T₁→⁶A₁ transition and shows, for this type of complex, the weak influence of the Mn²⁺ coordination and ThiaSO₂ conformation on this luminescence, the temperature and pressure dependence and quenching bymolecular dioxygen of which are reported for 2. The latter is attributed to energy transfer from the ⁴T₁ state exciting dioxygen to its ⁱΣ⁺ᵍ state and is responsible for the photosynthesis of the [(ThiaSO₂)(MnIII)(DMF)₂]Na (3) complex in DMF solution from 1 or 2. This reaction was studied by UV/Visible and EPR spectroscopy. The molecular structure and EPR spectroscopy of 3 are also presented.
Keywords: Thiacalixarene; Luminescence; Photooxidation; Manganese
European Journal of Inorganic Chemistry 2019(2019)1, 73-78
Strong and Selective Ni(II) Extractants Based on Synergistic Mixtures of Sulfonic Acids and Bidentate N-Heterocycles
Roebuck, J. W.; Bailey, P. J.; Doidge, E. D.; Fischmann, A. J.; Healy, M. R.; Nichol, G. S.; O'Toole, N.; Pelser, M.; Sassi, T.; Sole, K. C.; Tasker, P. A.
Bidentate 5,5ʹ-alkyl-3,3ʹ-bi-1H-pyrazole and 2-(5-alkyl-1H-pyrazol-3-yl)pyridine ligands, L⁵ and L⁶ , have been shown to be stronger synergists for the solvent extraction of Ni(II) from sulfate solutions by dinonylnaphthalene sulfonic acid (DNNSAH) than the structurally related tridentate ligand 2,6-bis-[5-n-nonylpyrazol-3-yl]pyridine, L¹ , previously reported by Zhou and Pesic. The bidentate ligands are highly selective, providing the option of sequential recovery of Ni(II) and Co(II) and rejection of other metals commonly found in the liquors resulting from the acidic sulfate leaching of laterite ores. They were the strongest synergists identified in a screening carried out on 18 types of bidentate and tridentate N-heterocyclic ligands, including the recently reported 2-(2ʹ-pyridyl)imidazoles, L⁹⁻¹¹ . X-ray crystal structures of Ni(II) complexes of model ligands for L⁵ and L⁶ , having t-butyl rather than long-chain alkyl groups and with 2-naphthalene sulfonate rather than DNNSA⁻ as counteranions, show that the [Ni(L)₃ ]²⁺ complexes form strong H-bonds from the pyrazolyl NH groups to the oxygen atoms of the sulfonate groups, an arrangement that will stabilize [Ni(L)₃ ·(DNNSA)₂ ] assemblies and shield their polar functionalities from diluent molecules of the water-immiscible phase. UV–visible spectra and mass spectrometry provide evidence for the strong synergists displacing all water molecules from the inner coordination sphere of the Ni(II) ions.
Keywords: Ni recovery; laterite processing; synergistic solvent extraction; outer-sphere bonding; supramolecular chemistry
Solvent Extraction and Ion Exchange 36(2019)5, 437-458
- Final Draft PDF 788 kB Secondary publication
Stationary beam full-field transmission helium ion microscopy using sub-50 keV He+: Projected images and intensity patterns
A dedicated Transmission Helium Ion Microscope (THIM) for sub-50 keV helium was developed to investigate ion scattering processes and contrast mechanisms to develop new imaging and analysis modalities. Unlike a commercial Helium Ion Microscope (HIM), the in-house built instrument allows full flexibility in experimental configuration. Here, we report transmission imaging and scattering patterns obtained from powder and bulk crystalline samples using a stationary broad-beam as well as convergent-beam illumination conditions in THIM. The scattered He+ ions formed unexpected spot patterns in the far-field for MgO, BN and NaCl powder samples, but not for Si bulk sample. The mechanistic origins of the spot patterns in these samples were investigated. Surface diffraction of ions was excluded as a possible cause because the recorded scattering angles do not correspond to the predicted Bragg angles. Complementary Secondary Electron (SE) imaging in a HIM revealed that these samples charge significantly under He+ ion irradiation. It is suggested that the spot patterns obtained in THIM experiments are artefacts related to sample charging. The results presented here indicate that factors other than channelling, blocking and surface diffraction of ions have an impact on the final scattered intensity distribution in the far-field. Hence, the different processes contributing to the final scattered intensities should be understood in more detail to decouple and study the relevant ion beam scattering phenomena.
Keywords: Helium Ion Microscopy; ion scattering; Transmission Ion Microscopy
Beilstein Journal of Organic Chemistry 10(2019), 1648-1657
Uranium(VI) Complexes of Glutathione Disulfide Forming in Aqueous Solution
The interactions between glutathione disulfide, GSSG, the redox partner and dimer of the intracellular detoxification agent glutathione, GSH, and hexavalent uranium, U(VI), were extensively studied by solution NMR, complemented by time-resolved laser-induced fluorescence and IR spectroscopies. As expected for the hard Lewis acid U(VI), coordination facilitates by the ligands’ O-donor carboxyl groups. However, owing to the adjacent cationic α-amino group, the glutamyl-COO reveal monodentate binding, while the COO of the glycyl residues show bidentate coordination. The log K value for the reaction UO₂2+ + H₃GSSG– = [UO₂H₃GSSG]+ (pH 3, 0.1 M NaClO₄) was determined for the first time, being 4.81 ± 0.08; extrapolation to infinite dilution gave log K° = 5.24 ± 0.08. U(VI) and GSSG form precipitates in the whole pD range studied (2 – 8), showing least solubility for 4 < pD < 6.5. Thus, particularly GSSG, hereby representing also other peptides and small proteins, affects the mobility of U(VI), strongly depending on the speciation of either component.
Keywords: uranium; uranyl; U(VI); glutathione; GSH; glutathione disulfide; GSSG; oxidized glutathione; complex; NMR; TRLFS; FT-IR; spectroscopy; stability constant
Inorganic Chemistry 59(2020)7, 4244-4254
- Secondary publication expected from 06.04.2021
Efficient calculation methods for the diffusion coefficient of interstitial solutes in dilute alloys
Wang, X.; Faßbender, J.; Posselt, M.
In the example of oxygen diffusion in dilute ferritic iron alloys it is shown that the calculation of the diffusion coefficient can be separated into a contribution related to the migration in the interaction region between oxygen and the substitutional solute and a part related to diffusion in pure bcc Fe. The corresponding diffusion times are determined by analytical expressions using Density-Functional-Theory (DFT) data for the respective binding energies. The diffusion coefficient in the interaction region must be determined by atomistic kinetic Monte Carlo (AKMC) simulations with DFT values for the migration barriers as inputs data. However, in contrast to previous calculations, AKMC simulation must be performed only for one concentration of the substitutional solute, and the obtained results can be employed to obtain data for other concentrations in a very efficient manner. This leads to a tremendous decrease of computational efforts. Under certain conditions it is even possible to use only analytical expression where merely DFT data for the binding energies are needed. The limits of applicability of the presented calculation procedures are discussed in detail. The methods presented in this work can be generalized to interstitial diffusion in other host materials with small concentrations of substitutional solutes.
Keywords: Diffusion coefficient; Interstitial solute; dilute alloy; Efficient calculation; First-principle calculations; Atomistic kinetic Monte Carlo simulations
Materials 12(2019)9, 1491
EUROMAT 2019, 01.-05.09.2019, stockholm, sweden
Defects and mechanical properties in weakly damaged Si ion implanted GaAs
Creutzburg, S.; Schmidt, E.; Kutza, P.; Loetzsch, R.; Uschmann, I.; Undisz, A.; Rettenmayr, M.; Gala, F.; Zollo, G.; Boulle, A.; Debelle, A.; Wendler, E.
Damage formation is investigated in GaAs implanted with 1 MeV Si ions to ion fluences from 3 × 10¹² to 5 × 10¹⁵ cm⁻² at room temperature. Under the conditions applied, amorphization of the implanted layers does not occur. The weakly damaged layers are studied by applying different experimental techniques including Rutherford backscattering spectrometry in channeling configuration, x-ray diffraction, in situ curvature measurement, optical subgap spectroscopy, and transmission electron microscopy. The results are evaluated and quantitatively connected with each other. Damage formation is described as a function of the ion fluence using a common defect evolution model. Point defects and defect clusters have to be taken into account in the ion fluence range of main interest up to 2 × 10¹⁵ cm⁻². Point defects contribute by a factor of about 8 more to both perpendicular strain and in-plane stress than defect clusters. When the concentration of point defects or the induced strain reaches a critical value, defect clusters form, which ensures that no further increase of perpendicular strain occurs. This reveals a clear driving force for cluster formation. The microstructure of the defect clusters cannot be determined from the results. As₃Ga₂ interstitial clusters are supposed. A remarkable decrease of the shear modulus of the implanted layers below the value of pristine GaAs by ≈ −35% is observed. Surprisingly, the change of shear modulus already sets in at a very low damage level of a few percent
Physical Review B 99(2019), 245205
Performance enhancement and characterization of liquid displacement battery having faradaic membrane
Mushtaq, K.; Zhao, J.; Weber, N.; Sadoway, D.
Übersicht über die Forschungsarbeiten zu "Liquid Displacement Batteries" am MIT, USA.
14th Workshop on Reactive Metal Processing, 15.03.2019, Boston, USA
Compliance-current-modulated resistive switching with multi-level resistance states in single-crystalline LiNbO3 thin film
Pan, X.; Shuai, Y.; Wu, C.; Luo, W.; Sun, X.; Zeng, H.; Guo, H.; Yuan, Y.; Zhou, S.; Böttger, R.; Cheng, H.; Zhang, J.; Zhang, W.; Schmidt, H.
Resistive switching behavior of a ca. 600 nm thick single-crystalline LiNbO3 (LNO) film has been investigated after vacuum-annealing. Oxygen vacancies (OVs) were generated in the LNO thin film during the annealing process. After electro-forming, filamentary resistive switching has been observed, and the performance of switching can be tuned by the compliance current level. Multi-level resistance states including four different low resistance states, were realized by setting different compliance currents, revealing that both concentration of OVs within the conductive filament and the geometry of the conductive filament influence the switching behavior. The conduction mechanisms of the charge transport during switching is discussed based on the current-voltage curves.
Solid State Ionics 334(2019), 1-4
Proton irradiation induced defects in β-Ga2O3: A combined EPR and theory study
Bardeleben, H.; Zhou, S.; Gerstmann, U.; Skachkov, D.; Lambrecht, W.; Ho, Q.; Deák, P.
Proton irradiation of both n-type and semi-insulating bulk samples of β-Ga2O3 leads to the formation of two paramagnetic defects with spin S = 1/2 and monoclinic point symmetry. Their high introduction rates indicate them to be primary irradiation induced defects. The first electron spin resonance (EPR1) has a g-tensor with principal values of gb = 2.0313, gc = 2.0079, and ga* = 2.0025 and quasi-isotropic superhyperfine interaction of 13G with two equivalent Ga neighbors. Under low temperature photoexcitation, this defect is quenched and replaced by a different metastable spin S = 1/2 center of comparable intensity. This second defect (EPR2) has similar principal g-values of gb = 2.0064, gc = 2.0464, and ga* = 2.0024 and shows equally superhyperfine interaction with two equivalent Ga atoms. This EPR2 defect is stable up to T = 100 K, whereas for T > 100 K the initial defect is recovered. Density functional theory calculations of the spin Hamiltonian parameters of various intrinsic defects are carried out using the gauge including projector augmented wave method in order to determine the microscopic structure of these defects. The intuitive models of undistorted gallium monovacancies or self-trapped hole centers are not compatible with neither of these two defects.
APL Materials 7(2019), 022521
Double-peak specific heat and spin freezing in the spin-2 triangular lattice antiferromagnet FeAl2Se4
Li, K.; Jin, S.; Guo, J.; Xu, Y.; Su, Y.; Feng, E.; Liu, Y.; Zhou, S.; Ying, T.; Li, S.; Wang, Z.; Chen, G.; Chen, X.
We report the properties of a triangular lattice iron-chalcogenide antiferromagnet FeAl2Se4.The spin susceptibility reveals a significant antiferromagnetic interaction with a Curie-Weiss temperature Θ_CW≃−200K and a spin-2 local moment. Despite a large spin and a large ∣Θ_CW∣, the low-temperature behaviors are incompatible with conventional classical magnets. No long-range order is detected down to 0.4 K. Similar to the well-known spin-1 magnet NiGa2S4, the specific heat of FeAl2Se4 exhibits a double-peak structure and a T2 power law at low temperatures, which are attributed to the underlying quadrupolar spin correlations and the Halperin-Saslow modes, respectively. The spin freezing occurs at ∼14 K, below which the relaxation dynamics is probed by the ac susceptibility. Our results are consistent with the early theory for the spin-1 system with Heisenberg and biquadratic spin interactions. We argue that the early proposal of the quadrupolar correlation and gauge glass dynamics may be well extended to FeAl2Se4. Our results provide useful insights about the magnetic properties of frustrated quantum magnets with high spins.
Physical Review B 99(2019), 054421
Oxyhydride Nature of Rare-Earth-Based Photochromic Thin Films
Cornelius, S.; Colombi, G.; Nafezarefi, F.; Schreuders, H.; Heller, R.; Munnik, F.; Dam, B.
Thin films of rare-earth (RE)−oxygen−hydrogen compounds prepared by reactive magnetron sputtering show a unique color-neutral photochromic effect at ambient conditions. While their optical properties have been studied extensively, the understanding of the relationship between photochromism, chemical composition, and structure is limited. Here we establish a ternary RE−O−H composition-phase diagram based on chemical composition analysis by a combination of Rutherford backscattering and elastic recoil detection. The photochromic films are identified as oxyhydrides with a wide composition range described by the formula REOxH3−2x where 0.5 ≤ x ≤ 1.5. We propose an anion-disordered structure model based on the face-centered cubic unit cell where the O2− and H− anions occupy tetrahedral and octahedral interstices. The optical band gap varies continuously with the anion ratio, demonstrating the potential of band gap tuning for reversible optical switching applications.
The Journal of Physical Chemistry Letters 10(2019), 1342-1348
Extension of the nodal code DYN3D to SFR applications
DYN3D is a well-established Light Water Reactor (LWR) simulation tool and is being extended for safety analyses of Sodium cooled Fast Reactors (SFRs) at the Helmholtz-Zentrum Dresden-Rossendorf. This thesis focuses on the first stage of the development process, that is, the extension and application of DYN3D for steady-state and transient SFR calculations on reactor core level. In contrast to LWRs, the SFR behavior is especially sensitive to thermal expansions of the reactor components. Therefore, a new thermal-mechanical module accounting for thermal expansions is implemented into DYN3D. At first step, this module is capable of treating two important thermal expansion effects occurring within the core, namely axial expansion of fuel rods and radial expansion of diagrid. In order to perform nodal calculations with DYN3D, pre-generated homogenized few-group cross sections (XS) are necessarily needed. Therefore, prior to the development of thermal expansion models, a general methodology for XS generation is established for SFR nodal calculations based on the use of the Monte Carlo code Serpent. The new methodological developments presented in this thesis are verified against the Monte Carlo solutions of Serpent. Two SFR cores are used for testing: the large oxide core of the OECD/NEA benchmark and a smaller core from the Phenix end-of-life tests. Finally, the extended DYN3D is validated against selected IAEA benchmark tests on the Phenix end-of-life experiments that contain both steady-state and transient calculations. The contribution to the SFR-related developments at the HZDR, as presented in this thesis, makes it possible of performing steady-state and transient calculations for SFRs on reactor core level by using DYN3D. With this study, the basis of the next stage of DYN3D developments is established, that is, the up-scale of SFR analysis to system level can continue by coupling with a sodium capable thermal-hydraulic system code.
Keywords: SFR; thermal expansion; group constant generation; nodal methods; spatial kinetics; Monte Carlo; Serpent; DYN3D
Lausanne, EPFL, 2019
Mentor: Pautz, Andreas; Fridman, Emil
Source term calculation and validation for F-18 production with a cyclotron for medical applications at HZDR
Konheiser, J.; Müller, S. E.; Magin, A.; Naumann, B.; Ferrari, A.
In this document we present the calculation and experimental validation of a source term for F-18 production with a cyclotron for medical applications operating at 18 MeV proton energy and 30 microA proton current. The Monte Carlo codes MCNP6 and FLUKA were used for the calculation of the source term. In addition, the radiation field around the O-18 enriched water target was simulated with the two codes. To validate the radiation field obtained in the simulation, an experimental program has been started using activation samples which are placed close to the water target during an F-18 production run of the cyclotron. After the irradiation, the samples are analyzed and the resulting activation is compared to Monte Carlo calculations of the expected sample activation. We and good agreement between simulations and experimental results, with most calculation to experiment (C/E) ratios well between 0.6 and 1.4.
Keywords: F-18; MCNP; FLUKA; Source Term; Cyclotron
Source term calculation and validation for F-18 production … (Id 28964) HZDR-primary research data are used by this publication
Journal of Radiological Protection 39(2019), 906-919
Fast-neutron-induced fission cross section of Pu(242) measured at the neutron time-of-flight facility nELBE
This dataset includes the processed data of the fast neutron-induced fission of Pu(242) experiement performed in November 2014 at the neutron time-of-flight facility nELBE which was published in T. Kögler et al., Phys. Rev. C 99, 024604
It contains the absolute (Pu242_nfis_Koegler_2019.csv) and relative (Pu242_U235_nfis_Koegler_2019.csv) cross section data ranging from 0.5 MeV to 10 MeV. The cross section data is given in comma separated ASCII files, as well as in a MS Excel-Sheet.
The columns of the tables are defined as follows:
- EN...neutron kinetic energy from the measured time of flight (ToF)
- EN-ERR...uncertainty of neutron kinetic energy = 0.5*(ToF bin width) = 1 ns
- DATA...cross section data
- ERR-S...statistical uncertainty of the cross section data
- ERR-SY...systematic uncertainty of the cross section data
- ERR-T...combined standard uncertainty of the cross section data
- ERR-0...relative uncertainty counting
- ERR-1...relative uncertainty normalization
- ERR-2...relative uncertainty reference cross section
- ERR-3...relative uncertainty FF detection inefficiency
- ERR-4...relative stat. uncertainty scattering correction H19
- ERR-5...relative sys. uncertainty scattering correction H19
- ERR-6...relative stat. uncertainty scattering correction PuFC
- ERR-7...relative sys. uncertainty scattering correction PuFC
Additionally, a root (see https://root.cern.ch/) file is supplied, including the determined cross sections and all nessessary data to reconstruct the experiment. This includes the measured quantities, reference data, correction factors, evaluated cross sections etc.
Keywords: neutron-induced fission; plutonium-242; cross section measurements; nuclear reactions; nucleon induced nuclear reactions; nELBE
Fast-neutron-induced fission cross section of Pu(242) … (Id 28878) has used this publication of HZDR-primary research data
Die Bestimmung des neutroneninduzierten Spaltquerschnitts … (Id 26338) has used this publication of HZDR-primary research data
Reseach data in the HZDR data repository RODARE
Publication date: 2019-03-06
Supplementary Data: Spectral Control via Multi-Species Effects in PW-Class Laser-Ion Acceleration
Supplementary materials for our paper "Spectral Control via Multi-Species Effects in PW-Class Laser-Ion Acceleration".
Additional high-resolution, raw HDF5 files using the openPMD standard (DOI:10.5281/zenodo.1167843) increase simulation output data to 4.7 TByte and are available from the corresponding author upon reasonable request.
Keywords: LPA; laser-ion acceleration; TNSA; multi-species; cryogenic target; particle-in-cell
Spectral Control via Multi-Species Effects in PW-Class … (Id 28962) has used this publication of HZDR-primary research data
Reseach data in the HZDR data repository RODARE
Publication date: 2019-03-06
Understanding the size effects on the electronic structure of ThO2 nanoparticles
Amidani, L.; Plakhova, T. V.; Romanchuk, A. Y.; Gerber, E.; Weiss, S.; Efimenko, A.; Sahle, C. J.; Butorin, S. M.; Kalmykovc, S. N.; Kvashnina, K. O.
Developing characterization techniques and analysis methods adapted to the investigation of nanoparticles (NPs) is of fundamental importance considering the role of these materials in many fields of research. The study of actinide based NPs, despite their environmental relevance, is still underdeveloped compared to that of NPs based on stable and lighter elements. We present here an investigation of ThO2 NPs performed with High-Energy Resolution Fluorescence Detected (HERFD) X-ray Absorption Near-Edge Structure (XANES) and with ab initio XANES simulations. Structural models of ThO2 NPs with sharp edges and corners reproduce the size effect observed in experimental data. Inspection of the simulations from Th atoms in the core and on the surface of the NP indeed demonstrates that the origin of the effect is the lowering of the number of coordinating atoms for Th at the surface of the NP. The sensitivity of HERFD XANES to the less coordinated atoms at the surface may be exploited to investigate surface interactions.
Physical Chemistry Chemical Physics 21(2019)20, 10635-10643
- Final Draft PDF 1,2 MB Secondary publication
Ion irradiation driven changes of magnetic anisotropy in ultrathin Co films sandwiched between Au or Pt covers
Modifications of magnetic anisotropy of 30 keV Ga + ion irradiated ultrathin Co films sandwiched between Au or Pt buffer and capping layers are investigated as a function of magnetic layer thickness, d Co , and the ion fluence, F. Maps (d Co , F) of saturation fields have been derived from local magnetooptical polar Kerr effect (PMOKE) measurements. The areas with increased remanent magnetization and/or saturation fields, which are directly related to the uniaxial anisotropy, adopt linear shapes for the two branches in the maps. They are very distinct, especially for the Pt/Co/Pt system irradiated at lower and higher fluence. Replacement of Pt with Au in the buffer layer results in minor influence on the magnetization properties of the irradiated trilayers. Au as a capping layer significantly decreases the anisotropy in the branch appearing at lower fluence. In the Au/Pt/Au sandwich, a severe reduction of induced anisotropy is observed in both branches. The proposed phenomenological model describing experimentally investigated magnetic anisotropies enables separation of surface and volume contributions to both branches of enhanced anisotropy.
Keywords: Chemical driving force demixing; Ion beam irradiation; Magnetooptics; Perpendicular magnetic anisotropy
Journal of Magnetism and Magnetic Materials 479(2019), 332
Digital LLRF Operation using MicroTCA at ELBE
Gümüş, Ç.; Hierholzer, M.; Kuntzsch, M.; Pfeiffer, S.; Schmidt, C.; Steinbrück, R.; Zenker, K.
The upgrade of the Low Level RF (LLRF) system of the Electron Linac for beams with high Brilliance and low Emittance (ELBE) at Helmholtz-Zentrum Dresden-Rossendorf (HZDR) was accomplished in 2018 . Now a digital system based on MTCA.4 can be used instead of the analogue system, which is operated since almost 20 years.The digital LLRF controller is implemented on a FPGA. The parametrisation and monitoring of the controller is performed by a ChimeraTK server application. ChimeraTK is a control system and hardware interface tool kit, which among others can provide an OPC-Unified Architecture (OPC-UA) interface. On the one hand, this interface is used to integrate the digital LLRF into the existing ELBE control and machine protection system, that is based on a Siemens PLC (S7) infrastructure. On the other hand, it is used to implement different additional clients of the ChimeraTK server application, such as the ELBE human machine interface used by the operators (WinCC, SCADA) or expert panels (e.g. LabView or Python). An overview of the new system including hardware as well as software components is given. In addition, an amplitude and phase noise measurement of a superconducting RF module are presented.
Invited lecture (Conferences)
5. Annual Matter and Technology Meeting, 05.-07.03.2019, Jena, Germany
SPECT-Untersuchungen mit dem 123 I-markierten Dopamintransporter-Liganden FP-CIT (DaTSCAN):DGN-Handlungsempfehlung (S1-Leitlinie)
Tatsch, K.; Buchert, R.; Bartenstein, P.; Barthel, H.; Boecker, H.; Brust, P.; Drzezga, A.; La Fougère, C.; Gründer, G.; Grünwald, F.; Krause, B.-J.; Kuwert, T.; Langen, K.-J.; Rominger, A.; Sabri, O.; Schreckenberger, M.; Meyer, P. T.
Die S1-Leitlinie soll bei der Indikationsstellung, Durchführung, Interpretation und Befundung von SPECT-Untersuchungen des Dopamintransporters (DAT) mit DaTSCANTM unterstützen.
Gegenüber der Vorgängerversion von 2007 berücksichtigt die vorliegende Aktualisierung und Überarbeitung die neuere wissenschaftliche Literatur, zwischenzeitlich veröffentlichte Guidelines der europäischen (EANM) und amerikanischen Fachgesellschaften (SNM), sowie die aktuelle Fassung der S3-Leitlinie „Idiopathisches Parkinson-Syndrom“ der Deutschen Gesellschaft für Neurologie. Zudem finden neue technische Möglichkeiten Berücksichtigung.
- Nuklearmedizin 58(2019)1, 5-16
Source term calculation and validation for F-18 production with a cyclotron for medical applications at HZDR
Data contained in Fig. 2 of the
Keywords: Cyclotron; Source term; MCNP6; FLUKA
Source term calculation and validation for F-18 production … (Id 28971) has used this publication of HZDR-primary research data
Reseach data in the HZDR data repository RODARE
Publication date: 2019-03-04
CFD-based optimization of heat exchanger tube bundle arrangement for passive spent fuel pool cooling to ambient air
Unger, S.; Beyer, M.; Krepper, E.; Hampel, U.
The storage of spent fuel in actively cooled water pools is common practice in nuclear power plants. One possibility to improve the reliability and the economy of spent fuel storage is the substitution of active cooling components by passive heat transfer systems. Thereby, ambient air should be the ultimate heat sink. A major drawback of natural convection heat transfer to ambient is the low heat transfer coefficient. Thus, bundle heat exchangers with finned tube are commonly employed. In one of our previous studies an optimum fin design was derived for such a heat exchanger. In the present investigation this tube bundle arrangement was numerical analysed with respect to optimal tube bundle configuration, tube shape, longitudinal tube pitch, transversal tube pitch and tube row number. We found highest heat transfer performance for oval shaped tubes with an axis ratio of 1:2.1 in a staggered configuration, having longitudinal tube pitch of 73 mm, a transversal tube pitch of 52 mm and 4 tube rows.
Contribution to proceedings
50th Annual Meeting on Nuclear Technology, 07.-08.05.2019, Berlin, Deutschland
Proceedings of the 50th Annual Meeting on Nuclear Technology
Spectral Control via Multi-Species Effects in PW-Class Laser-Ion Acceleration
Laser-ion acceleration with ultra-short pulse, PW-class lasers is dominated by non-thermal, intra-pulse plasma dynamics. The presence of multiple ion species or multiple charge states in targets leads to characteristic modulations and even mono-energetic features, depending on the choice of target material. As spectral signatures of generated ion beams are frequently used to characterize underlying acceleration mechanisms, thermal, multi-fluid descriptions require a revision for predictive capabilities and control in next-generation particle beam sources. We present an analytical model with explicit inter-species interactions, supported by extensive ab initio simulations. This enables us to derive important ensemble properties from the spectral distribution resulting from those multi-species effects for arbitrary mixtures. We further propose a potential experimental implementation with a novel cryogenic target, delivering jets with variable mixtures of hydrogen and deuterium. Free from contaminants and without strong influence of hardly controllable processes such as ionization dynamics, this would allow a systematic realization of our predictions for the multi-species effect.
Keywords: LPA; laser-ion acceleration; TNSA; multi-species; cryogenic target; particle-in-cell
Supplementary Data: Spectral Control via Multi-Species … (Id 28969) HZDR-primary research data are used by this publication
Laser-Plasma Accelerator Workshop 2019, 06.-10.05.2019, Split, Kroatien
Revealing the Nature of Photoluminescence Emission in Metal-Halide Double Perovskites
Zelewski, S. J.; Urban, J. M.; Surrente, A.; Maude, D. K.; Kuc, A.; Schade, L.; Johnson, R. D.; Dollmann, M.; Nayak, P. K.; Snaith, H. J.; Radaelli, P. G.; Kudrawiec, R.; Nicholas, R. J.; Plochocka, P.; Baranowski, M.
Double perovskite crystals such as Cs2AgBiBr6 are expected to overcome the limitation of classic hybrid organic-inorganic perovskite crystals related to the presence of lead and the lack of structural stability. Perovskites are ionic crystals in which the carriers are expected to strongly couple to lattice vibrations. In this work we demonstrate that the photoluminescence (PL) emission in Cs2AgBiBr6 is strongly influenced by the strong electron-phonon coupling. Combining photoluminescence excitation (PLE) and Raman spectroscopy we show that the PL emission is related to a color center rather than a band-to-band transition. The broadening and the Stokes shift of the PL emission from Cs2AgBiBr6 is well explained using a Franck-Condon model with a Huang-Rhys factor of S=11.7 indicating a strong electron-phonon interaction in this material.
Journal of Materials Chemistry C 7(2019)27, 8350-8356
- Final Draft PDF 421 kB Secondary publication
Effect of four lanthanides onto the viability of two mammalian kidney cell lines
Exposure to lanthanides (Ln) poses a serious health risk to animals and humans. Since Ln are mainly excreted with the urine, we investigated the effect of La, Ce, Eu, and Yb exposure on renal rat NRK-52E and human HEK-293 cells for 8, 24 and 48 h in vitro. Cell viability studies using the XTT assay and microscopic investigations were combined with solubility and speciation studies using ICP-MS and TRLFS. Thermodynamic modeling was applied to predict the speciation of Ln in the cell culture medium. All Ln show a concentration- and time-dependent effect on both cell lines with Ce being the most potent element. In cell culture medium, the Ln are completely soluble and most probably complexed with proteins from fetal bovine serum. The results of this study underline the importance of combining biological, chemical, and spectroscopic methods in studying the effect of Ln on cells in vitro and may contribute to the improvement of the current risk assessment for Ln in the human body. Furthermore, they demonstrate that Ln seem to have no effect on renal cells in vitro at environmental trace concentrations. Nevertheless, especially Ce has the potential for harmful effects at elevated concentrations observed in mining and industrial areas.
Keywords: f-elements; renal cells; cytotoxicity; XTT; time-resolved laser-induced fluorescence spectroscopy; thermodynamic modeling
Ecotoxicology and Environmental Safety 173(2019), 469-481
- Secondary publication expected
Improved axial plane distance and velocity determination for ultrafast electron beam X-ray computed tomography
Ultrafast electron beam X-ray computed tomography (UFXCT) has in recent years become an indispensable tool for multiphase flow studies. An essential feature of this technique is fast cross-sectional imaging in two distinct planes. Both the spatial location of focal spot path and detectors as well as the angular scanning range in UFXCT differ from that of conventional X-ray CT systems. This brings in a spatial dependence in axial scanning position and resolution. In this paper, we present an analysis of this problem, which results in an improved description of the location and shape of the imaging regions, a more accurate map of the distance between the imaging planes and finally a higher precision in the determination of axial structure velocities. The benefit of this improved approach is exemplarily demonstrated for a two-phase pipe flow around an obstacle.
Keywords: ultrafast X-ray computed tomography; phase velocity measurement
Measurement Science and Technology 30(2019)8, 084001
- Secondary publication expected
Transparent Conductive Tantalum Doped Tin Oxide as Selectively Solar-Transmitting Coating for High Temperature Solar Thermal Applications
The transparent conductive oxide (TCO) SnO2:Ta is developed as a selectively solar-transmitting coating for concentrated solar power (CSP) absorbers. Upon covering with an antireflective layer, a calculated absorptivity of 95 % and an emissivity of 30 % are achieved for the model configuration of SnO2:Ta on top of a perfect black body (BB). High-temperature stability of the developed TCO up to 1073 K is shown in situ by spectroscopic ellipsometry and Rutherford backscattering spectrometry. The universality of the concept is demonstrated by transforming silicon and glassy carbon from non-selective into solar-selective absorbers by depositing the TCO on top of them. Finally, the energy conversion efficiencies of SnO2:Ta on top of a BB and an ideal non-selective BB absorber are extensively compared as a function of solar concentration factor C and absorber temperature TH. Equal CSP efficiencies can be achieved by the TCO on BB configuration with approximately 50 % lower solar concentration. This improvement could be used to reduce the number of mirrors in a solar plant, and thus, the levelized costs of electricity for CSP technology.
Keywords: concentrated solar power; solar thermal electricity; solar-selective transmitter; transparent conductive oxide; high-temperature in situ characterization
Solar Energy Materials and Solar Cells 196(2019), 84-93
- Final Draft PDF 2,5 MB Secondary publication
Interstellar ⁶⁰Fe in Antarctica
Earth is constantly bombarded with extraterrestrial dust containing invaluable information about extraterrestrial processes, e.g. structure formation by stellar explosions or nucleosynthesis, which could be traced back by long-lived radionuclides. Here, we report the very first detection of a recent ⁶⁰Fe influx on Earth by analyzing 500 kg of snow from Antarctica by Accelerator Mass Spectrometry. By the measurement of the cosmogenically produced radionuclide ⁵³Mn, an atomic ratio of ⁶⁰Fe/⁵³Mn=0.017 was found, significantly above cosmogenic production. After elimination of possible terrestrial sources, such as global fallout, the excess of ⁶⁰Fe could only be attributed to interstellar ⁶⁰Fe from the solar neighborhood.
Keywords: AMS; supernova; ⁶⁰Fe
Physical Review Letters 123(2019), 072701
Critical dynamics of the Kuramoto model on sparse random networks
Juhász, R.; Kelling, J.; Ódor, G.
We consider the Kuramoto model on sparse random networks such as the Erdős-Rényi graph or its combination with a regular two-dimensional lattice and study the dynamical scaling behavior of the model at the synchronization transition by large-scale, massively parallel numerical integration. By this method, we obtain an estimate of critical coupling strength more accurate than obtained earlier by finite-size scaling of the stationary order parameter. Our results confirm the compatibility of the correlation-size and the temporal correlation-length exponent with the mean-field universality class. However, the scaling of the order parameter exhibits corrections much stronger than those of the Kuramoto model with all-to-all coupling, making thereby an accurate estimate of the order-parameter exponent hard. We find furthermore that, as a qualitative difference to the model with all-to-all coupling, the effective critical exponents involving the order-parameter exponent, such as the effective decay exponent characterizing the critical desynchronization dynamics show a non-monotonic approach toward the asymptotic value. In the light of these results, the technique of finite-size scaling of limited size data for the Kuramoto model on sparse graphs has to be treated cautiously.
Keywords: Networks; Kuramoto Model; Synchronization
Contribution to WWW
Journal of Statistical Mechanics: Theory and Experiment 5(2019), 053403
- Final Draft PDF 212 kB Secondary publication
Small-angle neutron scattering (SANS): Overview on principles and best practices
This talk provides an introduction into the method of small-angle neutron scattering (SANS), elements of good practice for the application and analysis as well as selected applications in the field of nuclear materials.
OECD/NEA Nuclear Science Committee Preparatory meeting: Best practices for nuclear materials characterisation techniques, 11.-12.02.2019, Boulogne-Billancourt, France
Critical synchronization dynamics of the Kuramoto model on connectome and small world graphs
Ódor, G.; Kelling, J.
The hypothesis, that cortical dynamics operates near criticality also suggests, that it exhibits universal critical exponents which marks the Kuramoto equation, a fundamental model for synchronization, as a prime candidate for an underlying universal model. Here, we determined the synchronization behavior of this model by solving it numerically on a large, weighted human connectome network, containing 804092 nodes, in an assumed homeostatic state. Since this graph has a topological dimension d<4, a real synchronization phase transition is not possible in the thermodynamic limit, still we could locate a transition between partially synchronized and desynchronized states. At this crossover point we observe power-law--tailed synchronization durations, with τt≃1.2(1), away from experimental values for the brain. For comparison, on a large two-dimensional lattice, having additional random, long-range links, we obtain a mean-field value: τt≃1.6(1). However, below the transition of the connectome we found global coupling control-parameter dependent exponents 1<τt≤2, overlapping with the range of human brain experiments. We also studied the effects of random flipping of a small portion of link weights, mimicking a network with inhibitory interactions, and found similar results. The control-parameter dependent exponent suggests extended dynamical criticality below the transition point.
Keywords: networks; brain; synchronization; kuramoto model
Kuramoto Model on KKI18 connectome (Id 29065) HZDR-primary research data are used by this publication
Contribution to WWW
Scientific Reports 9(2019), 19621
Framework modifications and dehydration path of a Ag+-modified, STI-type zeolite
Cametti, G.; Scheinost, A. C.; Giordani, M.; Churakov, S. V.
The effect of Ag+ incorporation into stellerite, a natural zeolite with STI framework type, was investigated by means of Single Crystal X-ray Diffraction (SC-XRD), Molecular Dynamics (MD) simulations and X-ray Absorption Fine Structure Spectroscopy (XAFS). At room temperature the complete exchange of the original extraframework ions with Ag+ provoked a distortion of the framework accompanied by symmetry reduction from orthorhombic Fmmm to monoclinic F2/m space group. Ag+ ions were strongly disordered, with occupancies ranging from 0.02 to 0.24, at partially-occupied sites within zeolitic cages. The combination of ab initio molecular dynamic simulations and XAFS spectroscopy suggested that Ag+ is coordinated by three water oxygens at 2.37 Å and by two framework oxygens at ca. 2.55 Å. The thermal stability was monitored in situ by SC-XRD (from 25 to 400°C) and by XAFS (from 25 to 650°C). Upon heating the structure transformed to three different topologies: B phase, D’ phase, observed here for the first time, and D phase. The unit-cell volume contracted from 4392.85(14) at room temperature to 3644.4(4) Å3, measured at 400°C. Possible Ag+ to Ag0 reduction could be excluded although the formation of Ag+-Ag+ clusters could not be unambiguously ruled out.
Keywords: zeolite; molecular dynamics; SC-XRD; XAFS; XANES; Ag
Journal of Physical Chemistry C 123(2019)22, 13651-13663
- Final Draft PDF 894 kB Secondary publication
Directed Evolution and Engineering of Gallium-Binding Phage Clones—A Preliminary Study
The phage surface display technology is a useful tool to screen and to extend the spectrum of metal-binding protein structures provided by nature. The directed evolution approach allows identifying specific peptide ligands for metals that are less abundant in the biosphere. Such peptides are attractive molecules in resource technology. For example, gallium-binding peptides could be applied to recover gallium from low concentrated industrial wastewater. In this study, we investigated the affinity and selectivity of five bacteriophage clones displaying different gallium-binding peptides towards gallium and arsenic in independent biosorption experiments. The displayed peptides were highly selective towards Ga3+ whereby long linear peptides showed a lower affinity and specificity than those with a more rigid structure. Cysteine scanning was performed to determine the relationship between secondary peptide structure and gallium sorption.
By site-directed mutagenesis, the amino acids of a preselected peptide sequence are systematically replaced by cysteines. The resulting disulphide bridge considerably reduces the flexibility of linear peptides. Subsequent biosorption experiments carried out with the mutants obtained from cysteine scanning demonstrated, depending on the position of the cysteines in the peptide, either a considerable increase in the affinity of gallium compared to arsenic or an increase in the affinity for arsenic compared to gallium. This study shows the impressive effect on peptide–target interaction based on peptide structure and amino acid position and composition via the newly established systematic cysteine scanning approach.
Keywords: phage surface display; gallium; metal–peptide interaction; site-directed mutagenesis; cysteine; peptide structure
Biomimetics 4(2019), 35
Nuclear level densities and gamma-ray strength functions in samarium isotopes
Naqvi, F.; Simon, A.; Guttormsen, M.; Schwengner, R.; Frauendorf, S.; Reingold, C. S.; Burke, J. T.; Cooper, N.; Hughes, R. O.; Humby, P.; Koglin, J.; Ota, S.; Saastamoinen, A.
The gamma-strength functions and level densities of in the quasi-continuum of 147,149Sm isotopes have been extracted from particle-gamma coincidences using the Oslo method. The nuclei of interest were populated via (p,d) reactions on pure 148,150Sm targets and the reaction products were recorded by the HYPERION array. An upbend in the gSF has been observed. The systematic analysis of the gSF for a range of Sm isotopes show that the scissors mode and the upbend compete with each other. Shell model calculations show a very good agreement with the experimental gSFs and confirm the competition between the upbend and scissors mode.
Keywords: Nuclear structure; light-ion reactions; gamma spectroscopy; level densities; strength functions; shell-model calculations
Physical Review C 99(2019), 054331
A proof of principle experiment for microbeam radiation therapy at the Munich Compact Light Source
Dombrowsky, A. C.; Burger, K.; Porth, A.-K.; Stein, M.; Dierolf, M.; Günther, B.; Achterhold, K.; Gleich, B.; Feuchtinger, A.; Bartzsch, S.; Beyreuther, E.; Combs, S. E.; Pfeiffer, F.; Wilkens, J. J.; Schmid, T. E.
Microbeam radiation therapy (MRT), a preclinical form of spatially fractionated radiotherapy, uses an array of microbeams of hard synchrotron X-ray radiation. Recently, compact synchrotron X-ray sources got more attention as they provide essential prerequisites for the translation of MRT into clinics while overcoming the limited access to synchrotron facilities. At the Munich Compact Light Source (MuCLS), a beamline at one of these novel compact X-ray sources, a proof of principle experiment was conducted applying MRT to a xenograft tumor mouse model. First, subcutaneous tumors derived from the established squamous carcinoma cell line FaDu were irradiated at a conventional X-ray tube using broadbeam geometry to determine a suitable dose range for the tumor growth delay.
For irradiations at the MuCLS, FaDu tumors were irradiated with broadbeam and microbeam irradiation at integral doses of either 3 or 5 Gy and tumor growth delay was measured. Microbeams had a width of 50 µm and a center-to-center distance of 350 µm with peak doses of either 21 or 35 Gy. A dose rate of up to 5 Gy/min was delivered to the tumor. Both doses and modalities delayed the tumor growth compared to a sham-irradiated tumor. The irradiated area and microbeam pattern were verified by staining of the DNA double-strand break marker γH2AX. This study demonstrates for the first time that microbeam radiation therapy can be successfully performed in vivo at the MuCLS.
Keywords: MRT; microbeam; compact source; tumor; X-rays; growth delay
Radiation and Environmental Biophysics (2020)
Online First (2019) DOI: 10.1007/s00411-019-00816-y
Time dependence of the bioassociation behavior of U(VI) and Eu(III) with Brassica napus cells
Jessat, J.; Sachs, S.; Moll, H.; Steudtner, R.; Bok, F.; Stumpf, T.
For both the remediation of contaminated sites and the safety assessment of nuclear waste repositories detailed knowledge about the transfer of radionuclides (RN) into the food chain is of central concern. The association of RN with plants and their interaction with released metabolites influences whose fate in the environment. We studied the time and concentration dependent bioassociation of U(VI) and Eu(III) as an analogue for trivalent actinides with Brassica napus cells. The aim was to determine the effect of both heavy metals on the cell viability and the influence of the cell metabolism on the speciation and bioavailability of both metals. Due to the exposure of the cells with Eu(III) and U(VI) a time and concentration dependent bioassociation behavior was observed. At 200 µM U(VI) a multistage bioassociation process occurred resulting in a detachment of bioassociated U(VI) back into the medium. This change in the U(VI) speciation in the medium was observed by time-resolved laser-induced fluorescence spectroscopy. The occurrence of three different U(VI) species in the medium over the exposure time (Fig. 1) indicates the release of plant cell metabolites, that can act as ligands for U(VI) complexation and may impact its transfer in the environment. Model calculations for the speciation of U(VI) in the initial medium were performed on basis of the literature . In order to identify possible plant cell metabolites, experiments on the enrichment and chromatographic separation of metabolites were carried out. In addition, the U(VI) complexation by relevant metabolites was studied.
 Sachs (2017) Environ. Sci. Technol. 51, 10843-10849.
Keywords: brassica napus; spectroscopy; species; TRLFS; bioassociation; metabolite; plant cells; Uranium; Europium
Goldschmidt 2019, 18.-23.08.2019, Barcelona, Spain
Goldschmidt 2019, 18.-23.08.2019, Barcelona, Spain
In vitro and in vivo Human Metabolism of (S)-[18F]Fluspidine – a Radioligand for Imaging σ1 Receptors with Positron Emission Tomography (PET)
Ludwig, F.-A.; Fischer, S.; Houska, R.; Hoepping, A.; Deuther-Conrad, W.; Schepmann, D.; Patt, M.; Meyer, P.; Hesse, S.; Becker, G.-A.; Zientek, F. R.; Steinbach, J.; Wünsch, B.; Sabri, O.; Brust, P.
(S)-[18F]fluspidine ((S)-[18F]1) has recently been explored for PET imaging of sigma-1 receptors in humans. In the current report, we have used plasma samples of healthy volunteers to investigate the radiometabolites of (S)-[18F]1 and elucidate their structures with LC-MS/MS. For the latter purpose additional in vitro studies were conducted by incubation of (S)-[18F]1 and (S)-1 with human liver microsomes (HLM). In vitro metabolites were characterized by interpretation of MS/MS fragmentation patterns from collision-induced dissociation or by use of reference compounds. Thereby, structures of corresponding radio-HPLC-detected radiometabolites, both in vitro and in vivo (human), could be identified. By incubation with HLM, mainly debenzylation and hydroxylation occurred, beside further mono- and di-oxygenations. The product hydroxylated at the fluoroethyl side chain was glucuronidated. Plasma samples (10, 20, 30 min p.i., n=5-6), obtained from human subjects receiving 250-300 MBq (S)-[18F]1 showed 97.2%, 95.4%, and 91.0% of unchanged radioligand, respectively. In urine samples (90 min p.i.) the fraction of unchanged radioligand was only 2.6% and three major radiometabolites were detected. The one with the highest percentage, also found in plasma, matched the glucuronide formed in vitro. Only a small amount of debenzylated metabolite was detected. In conclusion, our metabolic study, in particular the high fractions of unchanged radioligand in plasma, confirms the suitability of (S)-[18F]1 as PET radioligand for sigma-1 receptor imaging.
Keywords: Sigma-1 receptors (S1R); fluspidine; positron emission tomography (PET); radiometabolites; liquid chromatography-mass spectrometry (LC-MS); liver microsomes
Frontiers in Pharmacology 10(2019), 534
Selective histone deacetylase inhibitors as prospective radiotracers for PET imaging
Clauß, O.; Scheunemann, M.; Hansen, F. K.; Brust, P.
The class I histone deacetylases (HDACs) 1, 2 and 3 are overexpressed in several types of cancer, neurodegenerative diseases and inflammation. The catalyzed deacetylation of lysine residues on histones represents a key epigenetic modification that modulates the chromatin and thus influence the gene expression and transcription. Inhibition of zinc-dependent HDACs relaxes the chromatin structure and can result in transcriptional activation and anticancer effects, e.g. induction of apoptosis. Consequently, radiolabelled HDAC inhibitors have emerged as a potential tool for the diagnostic imaging of tumors by positron emission tomography (PET).
The aim of this work is the development of novel highly affine and selective fluorine containing derivatives of a class I selective HDAC inhibitor to obtain the corresponding 18-fluorine PET radiotracers with an ortho-aminoanilide as zinc-binding motif for targeting class I HDACs in tumors. A series of fluorinated reference compounds will be synthesized and the binding affinities and selectivities towards the HDAC isoforms 1, 2 and 3 will be determined. Our strategy is mainly focused on the medicinal chemistry of fluorine-containing derivatives, which are suitable for direct and indirect nucleophilic radiofluorination. For the most promising compounds, precursors for radiolabeling will be synthesized and a fully automated procedure will be established. The evaluation of physicochemical properties, e.g. stability and lipophilicity of the radiolabelled compounds will be assessed and further in vitro and in vivo investigations performed.
Keywords: Histone deacetylase inhibitors; Positron emission tomography; Fluorinated compounds
NCT Retreat 2019, 09.-10.05.2019, Heidelberg, Deutschland
Instability of precession driven Kelvin modes: Evidence of a detuning effect
Herault, J.; Giesecke, A.; Gundrum, T.; Stefani, F.
We report an experimental study of the instability of a nearly resonant Kelvin mode forced by precession in a cylindrical vessel. The instability is detected above a critical precession ratio via the appearance of peaks in the temporal power spectrum of pressure fluctuations measured at the end walls of the cylinder. The corresponding frequencies can be grouped into frequency sets satisfying resonance conditions with the forced Kelvin mode. We show that one set forms a triad that is associated with a parametric resonance of Kelvin modes. We observe a significant frequency variation of the unstable modes with the precession ratio, which can be explained by a detuning mechanism due to the slowdown of the background flow. By introducing a semianalytical model, we show that the departure of the flow from the solid body rotation leads to a modification of the dispersion relation of Kelvin modes and to a detuning of the resonance condition. The second frequency set includes a very low frequency and does not exhibit the properties of a parametric resonance between Kelvin modes. Interestingly, this frequency set always emerges before the occurrence of the triadic resonances, i.e., at a lower precession ratio, which implies that it may correspond to a different type of instability. We discuss the relevance of an instability of a geostrophic mode described by Kerswell [Kerswell, J. Fluid Mech. 382, 283 (1999)], although other mechanisms cannot be completely ruled out.
Keywords: Precession; Dynamo; DRESDYN
Physical Review Fluids 4(2019), 033901
Limited importance of EphrinA1–ligand, Src kinase, and focal adhesion kinase in EphA2-mediated regulation of metastasis in Mel-Juso and A375 human melanoma cells
EphA2 receptor tyrosine kinase fulfils various functions in the development of cancers. Here we analyzed how regulation of EphA2 receptor influences metastatic properties in human melanoma cells in vitro and lung metastasis in vivo. Further, we investigated whether the effects are mediated by Src kinase/focal adhesion kinase (FAK) signaling downstream of EphA2. Therefore, as model Mel-Juso and A375 melanoma cell lines showing different intrinsic EphA2 expression levels were used. To regulate EphA2 expression and activity, we used RNA interference, transgeneic EphA2 overexpression, and stimulation of EphA2 activity by adding EphrinA1. Adhesion to fibronectin was increased in EphA2-silenced cells and decreased in EphA2-overexpressing cells. Migration and planar motility were unaffected in Mel-Juso cells, but increased in EphA2-silenced A375 cells and decreased in EphA2-overexpressing A375 cells. Adhesion and migration were unaffected by EphrinA1-stimulation, indicating ligand-independent mechanisms. In vivo we detected increased lung metastasis in mice inoculated with EphA2-overexpressing Mel-Juso cells, substantiating the pro-metastatic effects of EphA2 in melanoma. Activity of Src kinase and FAK were unaffected in EphA2-silenced cells and in response to EphrinA1-stimulation. However, in EphA2-overexpressing A375 cells Src phosphorylation was increased, indicating enhanced Src activity. Together, these data suggest that EphA2 receptor promotes malignancy ligand-independently by mechanisms different from Src kinase/FAK signaling.
Keywords: Cellular adhesion; cellular migration; Eph receptor tyrosine kinases; Ephrins; malignant skin cancer; metastatic melanoma; RNA interference
Journal of Cellular Biotechnology 5(2019)1, 11-26
- Secondary publication expected
Regulation of A375 melanoma cell adhesion and migration by EphB4 and EphrinB2 –insights from co-culture experiments
BACKGROUND: Malignant melanoma is the most malignant skin neoplasm due to early metastasis and resistance to currently available therapies. Inflammatory tumor infiltrate, particularly macrophages, are of outstanding importance for melanoma progression and therapy response. EphB4 receptor and its preferred ligand EphrinB2 are also associated with melanoma progression, metastasis, and therapy resistance.
OBJECTIVE: The aim of our study was to systematically investigate the role of EphB4 for melanoma cell adhesion and migration, also in the presence of macrophages, considering experimental i) EphB4 overexpression, ii) EphB4 activation, iii) inhibition of EphB4 and EphrinB2 interaction, and iv) inhibition of EphB4 and downstream signaling.
RESULTS: Overexpression of EphB4 resulted in increased A375 melanoma cell adhesion showing EphrinB2 reverse signaling rather than EphB4 forward signaling being responsible. By contrast, A375 melanoma cell migration was not affected by EphB4 overexpression and effects due to modulation of EphB4/EphrinB2 signaling were inconsistent. In co-culture experiments macrophages (HL-60(M)) showed substantial influence on adhesion and migration of A375 cells. However, HL-60(M)-mediated effects could not be assigned to EphB4/EphrinB2 signaling but rather to cytokine signaling pathways.
CONCLUSIONS: Under the used experimental settings EphB4 is important for adhesion but not for the migration of A375 melanoma cells. Macrophages influenced adhesion and migration of melanoma cells but without significant involvement of EphB4/EphrinB2 signaling.
Keywords: Eph receptor tyrosine kinases; Ephrin ligands; malignant melanoma; metastasis; tumor microenvironment; tyrosine kinase inhibitors
Journal of Cellular Biotechnology 5(2019)1, 27-42
- Secondary publication expected
Linear damped interfacial wave theory for an orbitally shaken upright circular cylinder
We present a new theoretical model describing gravity-capillary waves in orbitally shaken cylindrical containers. Our model can account for both one-layer free surface and two-layer interfacial wave systems. A set of modal equations for irrotational waves is formulated that we complement with viscous damping rates to incorporate energy dissipation. This approach allows us to calculate explicit formulas for the phase shifts between wave and shaker which are practically important for the mixing efficiency in orbitally shaken bioreactors. Resonance dynamics are described using eight dimensionless numbers revealing a variety of different effects influencing the forced wave amplitudes. As an unexpected result, the model predicts the formation of novel spiral wave patterns resulting from a damping-induced symmetry breaking mechanism. For validation we compare theoretical amplitudes, fluid velocities and phase shifts with three different and independent experiments and - when using the slightly deviating experimental values of the resonance frequencies - find a good agreement within the theoretical limits.
Journal of Fluid Mechanics 891(2020), A22
Zeit- und Konzentrationsabhängigkeit des Bioassoziationsverhaltens von U(VI) und Eu(III) mit Brassica napus-Zellen
Jessat, J.; Sachs, S.; Moll, H.; Steudtner, R.; Bok, F.; Stumpf, T.
Sowohl im Hinblick auf die Sanierung radioaktiv kontaminierter Flächen als auch für die Sicherheitsbeurteilung von potentiellen Endlagern für radioaktive Abfälle wird detailliertes Wissen über das Transferverhalten von Radionukliden (RN) in der Umwelt benötigt, da diese in die Nahrungskette gelangen können und damit ein Gesundheitsrisiko für Menschen darstellen. Die Bioassoziation von RN mit Pflanzen und ihre Wechselwirkung mit in den Boden freigesetzten Pflanzenmetaboliten kann deren Verbleib in der Umwelt beeinflussen. Es ist bekannt, dass die Aufnahme und Vertei-lung der RN in Pflanzen und damit ihre Bioverfügbarkeit signifikant von der vorliegenden Metallspeziation bestimmt wird . Es wurden die Zeit- und Konzentrationsabhängigkeit des Bioassoziationsverhaltens von U(VI) und Eu(III) als Analogon für dreiwertige Actinide mit Brassica napus (Raps)-Zellen untersucht. Ziel dieser Arbeiten war es, den Effekt beider Schwermetalle auf die Zellvitalität sowie den Einfluss des Zellmetabolismus auf die Speziation beider Metalle zu bestimmen. Es konnte ein zeit- und konzentrationsabhängiges Bioassoziationsverhalten bei Exposition der Zellen mit U(VI) und Eu(III) beobachtet werden. In Gegenwart von 200 µM U(VI) tritt ein mehrstufiger Bioassoziationsprozess auf, bei dem es zur Freisetzung des zuvor bioassoziierten U(VI) in das umgebende Nährmedium kommt. Damit einhergehend konnte mittels zeitaufgelöster laser-induzierter Fluoreszenzspektroskopie eine Speziationsveränderung nachvollzogen werden. Dabei wurden drei unterschiedliche U(VI)-Spezies (s. Abb. 1) im Nährmedium nachgewiesen, die Hinweise auf die Freisetzung von Pflanzenzellmetaboliten liefern. Diese können als Liganden für die U(VI)-Komplexierung fungieren und damit einen Einfluss auf das Transferverhalten von U(VI) in der Umwelt haben. Die U(VI)-Speziation im Ausgangsnährmedium wurde in Anlehnung an die Literatur thermodynamisch modelliert . Um mögliche Metabolite zu identifizieren, wurden Experimente zur Anreicherung und chromatographischen Trennung von Metaboliten durchgeführt. Zudem wurde die U(VI)-Komplexierung mit relevanten Metaboliten untersucht.
 S. Ebbs et al., J. Exp. Bot. 1998, 49, 1183-1190.  S. Sachs et al., Environ. Sci. Technol. 2017, 51, 10843-10849.
Keywords: Pflanzen; Brassica napus; Raps; Metabolite; Suspensionszellen; Uran; Europium; Toxizität; Speziation; Komplexierung
Jahrestagung der Fachgruppe Nuklearchemie 2019, 25.-27.09.2019, Dresden, Deutschland
Mass separated Focused Ion Beams from Liquid Metal Alloy Ion Sources
Focused Ion Beam (FIB) processing has been developed into a well-established and still promising technique in nearly all fields of nano-technology in particular for direct patterning and proto-typing on the µm scale and well below. Beside new ion source developments based on gas field emission (GFIS), on ionic liquids (ILIS), on magneto-optical traps (MOTIS) or on ICP or ECR sources for Xe-FIB as well as the nearly exclusively used gallium Liquid Metal Ion Sources (LMIS), the replacement of Ga by alloys therein with an adapted FIB optics design can open bright field of new employments. Local ion implantation, ion beam mixing, ion beam synthesis or Focused Ion Beam Lithography (IBL) in the µm- or nm range can benefit from ion species purposely selected in parallel to gallium or noble gases. Therefore, exploring the Liquid Metal Alloy Ion Sources (LMAIS) potential represent a promising alternative to expand the global FIB application fields. Especially, IBL as direct, resistless and three-dimensional patterning enables a simultaneous in-situ process control by cross-sectioning and inspection. Thanks to this nearly half of the elements of the periodic table are made available in the FIB technology as a result of continuous research in this area during the last forty years. Key features of a LMAIS are long life-time, high brightness and stable ion current. Recent developments could make these sources as an alternative technology feasible for nano patterning challenges e.g. to tune electrical, optical, magnetic or mechanic properties.
In this contribution the operation principle, the preparation and testing technology as well as prospective domains for modern FIB applications will be presented. As an example we will introduce a Ga35Bi60Li5 LMAIS in detail. It enables high resolution imaging with light Li ions and sample modification with Ga or heavy polyatomic Bi clusters, all coming from one ion source.
L. Bischoff, P. Mazarov, L. Bruchhaus, and J. Gierak, Appl. Phys. Rev. 3, 021101 (2016).
Keywords: Liquid Metal Alloy Ion Source; Focused Ion Beam; Mass spectra; Cluster ions
PicoFIB - The International Network for gas Ion Patterning and Microscopy, 13.02.2019, London, Great Britain
Compositional Multi-Point Geostatistics for Tailings Deposits - A Synthetic Case Study
Selia, S. R. R.; Tolosana-Delgado, R.; van den Boogaart, K. G.; Schaeben, H.
Currently tailings deposits have become new resources that are challenging and valuable to exploit. To properly exploit them, we require a 3D spatial characterization of their mineral content. In a natural deposit, this is achieved by sampling at several locations and applying geostatistics to estimate block values. Certain characteristics of tailings deposits make them not amenable to conventional geostatistics. In particular, it is important to consider both valuable and gangue minerals, thus we need to take the compositional nature of our variables into account. In addition, the interplay of erosional and depositional processes creates structures with certain continuity patterns that cannot be modelled by conventional variogram-based methods such as kriging.
Therefore, we use a Multi-Point Geostatistics method, Direct Sampling (DS). DS is based on selecting the event from a training image, the conceptual spatial arrangement of a variable, with the shortest distance to the data event from the simulation domain. To account for the compositional nature of our variables, the Aitchison distance is calculated. We use numerical stratigraphic modelling to obtain a variety of training images, which we feed into a modified DS to deal with multiple training images at once.
We tested the proposal on a multi-source synthetic tailings deposit produced by numerical stratigraphic processes. Each grid of the model contains information about the content of several sediment species summing to 100%. Hard data are sampled on the model at certain locations and along with several unique training images we recreate the full 3D spatial distribution of the properties.
Keywords: Conditional simulation; Tailings Characterization; Remining
5th International Young Earth Scientist Network (YES) Congress 2019, 09.-13.09.2019, Berlin, Germany
Radiochemical and radiopharmacological characterization of a 64Cu-labeled α-MSH analog conjugated with different chelators
Radiolabeled α-melanocyte stimulating hormone (α-MSH) derivatives have a high potential for diagnosis and treatment of melanoma, due to high specificity and binding affinity to the melanocortin-1 receptor (MC1R). Hence, the α-MSH-derived peptide NAP-NS1 with a β-Ala linker (ε-Ahx-beta-Ala-Nle-Asp-His-D-Phe-Arg-Trp-Gly-NH2) was conjugated to different chelators: either to NOTA (p-SCN-Bn-1,4,7-triazacyclononane-1,4,7-triacetic acid), to a hexadentate bispidine carbonate derivative (dimethyl-9-(((4-nitrophenoxy)carbonyl)oxy)-2,4-di(pyridin-2-yl)-3,7-bis(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate) or to DMPTACN (p-SCN-Ph-bis(2-pyridyl-methyl)-1,4,7-triaza-cyclononane), labeled with 64Cu and investigated in terms of radiochemical and radiopharmacological properties.
For the three 64Cu-labeled conjugates negligible transchelation, suitable buffer and serum stability, as well as appropriate water solubility was determined. The three conjugates exhibited high binding affinity (low nanomolar range) in murine B16F10, human MeWo and human TXM13 cells. The Bmax values of [64Cu]Cu-bispidine-NAP-NS1 ([64Cu]Cu-2) and [64Cu]Cu-DMPTACN-NAP-NS1 ([64Cu]Cu-3) were higher than those of [64Cu]Cu-NOTA-NAP-NS1 ([64Cu]Cu-1), implying that different charged chelate units might have an impact on binding capacity. Preliminary in vivo biodistribution studies suggested the main excretion pathway of [64Cu]Cu-1 and [64Cu]Cu-3 to be renal, while that of [64Cu]Cu-2 seemed to be both renal and hepatobiliary. An initial moderate uptake in the kidney decreased clearly after 60 min. All three 64Cu-labeled conjugates should be considered for further in vivo investigations using a suitable xenograft mouse model.
Keywords: copper chelators; melanocortin-1 receptor; α-MSH; malignant melanoma; molecular imaging; radiopharmaceuticals; radiotracer; PET
Journal of Labelled Compounds and Radiopharmaceuticals 62(2019)8, 495-509
Influence of calcium on uranium and neptunium sorption on clay minerals at (hyper)alkaline conditions
Philipp, T.; Schmeide, K.; Stumpf, T.
Our previous experiments have shown that U(VI) is retained very strongly by Ca-bentonite in the pH range 10-12. Different spectroscopic techniques (site-selective TRLFS, EXAFS) have proven that the underlying retention mechanism under the given conditions was adsorption (not precipitation) despite the negative mineral surface charge and the anionic character of prevailing aqueous U(VI) species. It was hypothesized that attachment is facilitated by mediating calcium cations which are present in the solution. Therefore, the influence of calcium on the sorption of U(VI), Np(V) and Np(VI) at alkaline conditions was systematically studied. These radionuclides were selected as their aqueous speciation at high pH values is characterized by the predominance of anionic hydroxide species. Furthermore the adsorption of 45Ca on clay minerals and the resulting effect on the mineral surface charge was examined.
It was found that 45Ca adsorbed almost completely on Ca-bentonite between pH 8 and 13. Zeta potential measurements showed a partial compensation of the strongly negative surface charge of Ca-bentonite upon introduction of calcium. Hence, calcium is present at the surface, offering possible sorption sites for anionic uranium and neptunium species. Batch sorption experiments at different calcium concentrations revealed enormous effects on the retention of U(VI), Np(V) and Np(VI) between pH 10 and 13. Exemplarily shown for U(VI) in the figure below, the strong retention could not be observed in the experiment with kaolinite, where calcium was completely absent. Consequently, calcium is a crucial factor for the safety assessment of deep geological radioactive waste repositories, where (hyper)alkaline conditions evolve due to cement degradation.
Keywords: Calcium; U(VI); Np(V); Np(VI); adsorption; surface charge
2nd International Conference on Radioanalytical and Nuclear Chemistry, 05.-10.05.2019, Budapest, Ungarn
Plasmonic field guided patterning of ordered colloidal nanostructures
Huang, X.-P.; Chen, K.; Qi, M.-X.; Zhang, P.-F.; Li, Y.; Winnerl, S.; Schneider, H.; Yang, Y.; Zhang, S.
Nano-patterned colloidal plasmonic metasurfaces are capable of manipulation of light at the subwavelength scale. However, achieving controllable lithography-free nano-patterning for colloidal metasurfaces still remains a major challenge, limiting their full potential in building advanced plasmonic devices. Here, we demonstrate plasmonic field guided patterning (PFGP) of ordered colloidal metallic nano-patterns using orthogonal laser standing evanescent wave (LSEW) fields. We achieved colloidal silver nano-patterns with a large area of 30 mm² in <10 min by using orthogonal LSEW fields with a non-focused ultralow fluence irradiation of 0.25 W cm⁻². The underlying mechanism of the formation of the nanopatterns is the light-induced polarization of the nanoparticles (NPs), which leads to a dipole-dipole interaction for stabilizing the nano-pattern formation, as confirmed by polarization-dependent surface-enhanced Raman spectroscopy. This optical field-directed self-assembly of NPs opens an avenue for designing and fabricating reconfigurable colloidal nano-patterned metasurfaces in large areas.
Keywords: ordered colloidal nanostructures; plasmonic field guided patterning; polarization stabilizing
Nanophotonics 8(2019)3, 505-512
Fluorescent Mouse Pheochromocytoma Spheroids Expressing Hypoxia-Inducible Factor 2 alpha: Morphologic and Radiopharmacologic Characterization
BACKGROUND: Pheochromocytomas and paragangliomas (PPGLs) are rare catecholamine-producing tumors arising from chromaffin tissue. In a PPGL subgroup, dysregulation of hypoxia signaling pathways, in particular mediated through stabilization of hypoxia-inducible factor 2 alpha (HIF2α), have been suggested to drive tumorigenesis through altering downstream transcriptional activity.
OBJECTIVE: This study evaluated the use of mCherry-transgenic mouse pheochromocytoma (MPCmCherry) spheroids as in vitro models for investigating consequences of HIF2α expression on aggregation behavior, morphology, growth, glucose consumption, amino acid uptake, and somatostatin type 2 receptors under stable hypoxic conditions.
METHODS: MPCmCherry spheroids were monitored using confocal laser scanning microscopy. Hypoxic regions were detected using pimonidazole. Radiotracer incubation was performed using 2 [18F]fluoro-2-deoxyglucose ([18F]FDG), O 3 (2[18F]fluoroethoxy)-4 hydroxyphenylalanine ([18F]OFED), and [68Ga]Ga (Tyr3)octreotate ([68Ga]Ga-DOTA-TATE).
RESULTS: Both HIF2α-expressing and empty vector (EV) control spheroids showed regions of stable cellular hypoxia. Expression of HIF2α in MPCmCherry spheroids was associated with less symmetric morphology, faster growth, and decreased uptake of [68Ga]Ga DOTA-TATE (somatostatin type 2 receptors) compared to controls, whereas, uptake of [18F]FDG (glucose transporter 1 and hexokinases) and [18F]OFED (system L amino acid transporter 1) remained unaffected.
CONCLUSIONS: The recent study proved MPCmCherry spheroids to be complex three-dimensional tumor cell models for investigating morphologic and metabolic consequences of dysregulated hypoxia pathways under hypoxic conditions.
Keywords: Amino acid transporters; Confocal laser scanning microscopy; Neuroendocrine tumors; Paraganglioma; Pimonidazole; Positron emitters; Radiotracer uptake; Somatostatin receptors
Journal of Cellular Biotechnology 5(2019)2, 135-151
- Secondary publication expected from 30.12.2020
Investigation of [18F]FESCH for PET imaging of the adenosine A2A receptor in a rotenone-based mouse model of Parkinson´s disease and development of a two-step one-pot radiolabeling strategy
Schröder, S.; Lai, T. H.; Kranz, M.; Toussaint, M.; Shang, Q.; Dukic-Stefanovic, S.; Pan-Montojo, F.; Brust, P.
Rotenone-treated mice are regarded as a model for Parkinson´s disease (PD). Increased availability of the adenosine A2A receptor (A2AR) has been found in the striatum of patients with PD and dyskinesias . The aim of this study was to investigate whether similar alterations are found in the mouse model of PD using small animal PET/MR imaging. For that purpose, [18F]FESCH  was the radiotracer of choice due to its high A2AR specificity and excellent PET imaging properties [2-5]. Furthermore, we intended to develop a simplified one-pot strategy for the radiosynthesis of [18F]FESCH.
The published two-step procedures for the radiosynthesis of [18F]FESCH start with the nucleophilic 18F-labeling of ethane-1,2-diol bis(3,4-dibromobenzenesulfonate)  or ethane-1,2-diol bis(4-methylbenzenesulfonate) . The respective [18F]fluoroethyl synthon is isolated either by semi-preparative HPLC  or cartridge  and, only then, reacted with the phenol precursor desmethyl SCH442416. In our novel one-pot approach, desmethyl SCH442416 was treated with 40% TBAOHaq. to generate the activated phenolate which was directly reacted with the non-isolated 2-[18F]fluoroethyl tosylate in MeCN at 120 °C for 10 min (see Figure 1). [18F]FESCH was purified by semi-preparative HPLC, concentrated using solid-phase extraction on a pre-conditioned RP cartridge and eluted with absolute EtOH. After evaporation of the solvent at 75 °C, the radiotracer was finally formulated in isotonic saline ready for injection. [18F]FESCH (5.0±1.8 MBq) was administered to C57BL/6JRj mice (control n=5, rotenone-treated n=7, 18 month, 28-35 g) and whole body scans were performed for 60 min in listmode with a Mediso nanoScan® PET/MR scanner followed by dynamic reconstruction. Time-activity curves (TACs) were generated for regions of interest such as striatum (Figure 1) and cerebellum as reference region.
The herein described one-pot strategy provided [18F]FESCH (Ki hA2A=0.6 nM) with an overall radiochemical yield of 16.1±1.5% (n=9, EOB), a radiochemical purity of ≥98% and compared to the published two-pot procedure with a notably increased molar activity of 116±18.5 GBq/µmol (n=7, EOS). The PET images over 60 min showed high uptake of [18F]FESCH in the striatum (Figure 1) which is consistent with the known A2AR distribution pattern in the brain. Although not significant, slightly higher striatal A2AR binding was found in rotenone-treated mice.
The radiotracer [18F]FESCH proved to be suitable for in vivo imaging of the adenosine A2A receptor in the mouse brain. Since the increased A2AR availability appears to be related to dyskinesia, it has to be proven whether the investigated mouse model of PD reflects this aspect.
The European Regional Development Fund (ERDF) and Sächsische Aufbaubank (SAB) are acknowledged for financial support (Project No. 100226753).
 Ramlackhansingh et al., Neurology, 76, 2011
 Khanapur et al., J. Med. Chem., 57, 2014
 Shinkre et al., Bioorg. Med. Chem. Lett., 20, 2010
 Bhattacharjee et al., Nucl. Med. Biol., 38, 2011
 Khanapur et al., J. Nucl. Med., 58, 2017
23rd International Symposium on Radiopharmaceutical Sciences (ISRS 2019), 26.-31.05.2019, Beijing, China
Entwicklung einer Eintopf-Radiosynthese von F-18-FESCH für die PET-Bildgebung des Adenosin-A2A-Rezeptors im Rotenon-basierten Parkinson-Mausmodel
Schröder, S.; Lai, T. H.; Deuther-Conrad, W.; Dukic-Stefanovic, S.; Kranz, M.; Toussaint, M.; Shang, Q.; Pan-Montojo, F.; Brust, P.
Gegenstand der Studie ist es, das Expressionsmuster des Adenosin-A2A-Rezeptors im Gehirn von Wildtyp(WT)- und Parkinsonmodel-Mäusen mittels KleintierPET/MRT zu untersuchen. Zu diesem Zweck wurde F-18-FESCH (1) als geeigneter A2A-Radiotracer ausgewählt, wobei eine vereinfachte Methode zur Radiosynthese entwickelt werden sollte.
In der publizierten zweistufigen Radiosynthese von F-18-FESCH wird das verwendete F-18-Fluorethylsynthon mittels Festphasenextraktion (1) oder semi-präparativer HPLC (2) isoliert und erst dann mit dem Phenol-Präkursor umgesetzt. In der hier entwickelten Eintopf-Methode wurde der Phenol-Präkursor mittels TBAOHaq. deprotoniert und direkt zur Reaktionsmischung des F-18-Fluorethylsynthons zugegeben. Die F-18-Fluorethylierung erfolgte in MeCN bei 120°C für 10 min. F-18-FESCH wurde mittels semi-präparativer HPLC isoliert, über eine RP18-Kartusche konzentriert und in 0,9%iger NaClaq. formuliert. Der Radiotracer (4-8 MBq) wurde C57BL/6JRj-Mäusen (WT n=5, Rotenon-behandelt n=7, 18 Monate) appliziert und Ganzkörperscans mit einem Mediso nanoScan® PET/MRT aufgenommen.
F-18-FESCH (Ki hA2A=0,6 nM) wurde mit einer radiochemischen Ausbeute von 16,1±1,5% (n=9, EOB), einer radiochemischen Reinheit von ≥98% und einer im Vergleich zur Literatur deutlich gesteigerten molaren Aktivität von 116±18,5 GBq/µmol (n=7, EOS) bereitgestellt. Die summierten PET-Bilder (1 h) zeigen eine erhöhte Anreicherung von F-18-FESCH im Striatum, wobei kein signifikanter Unterschied zwischen den WT- und Rotenon-behandelten Mäusen detektiert wurde.
F-18-FESCH ist zur PET-Bildgebung des A2A-Rezeptors im Maushirn geeignet. Die ersten Ergebnisse der PET-Studie im Parkinson-Mausmodel weisen auf keine veränderte A2A-Rezeptordichte hin.
(1) Khanapur et al., J. Med. Chem., 57, 2014
(2) Bhattacharjee et al., Nucl. Med. Biol., 38, 2011
57. Jahrestagung der Deutschen Gesellschaft für Nuklearmedizin e.V.(NuklearMedizin 2019), 03.-06.04.2019, Bremen, Deutschland
Experimental and theoretical investigation of the boiling heat transfer in a low pressure natural circulation system
Viereckl, F.; Schleicher, E.; Schuster, C.; Lippmann, W.; Hurtado, A.
The implementation of passive safety systems in nuclear reactors provide the opportunity to enhance the nuclear safety. On the other hand, an accurate and reliable prediction of the heat removal behavior is not ensured because the operating conditions of certain types of passive systems like containment cooling systems differ from the validity ranges of the established heat transfer correlations. Therefore, a generic and detailed investigation is still necessary for passive systems.
Against this background, the test facility GENEVA was erected at Technische Universität Dresden in 2012. Since the commissioning, generic experiments concerning the system and stability behavior of this facility, which emulates a low pressure and low flow (LPLF) natural circulation system, were provided. Nevertheless, the investigation of the heat transfer behavior remained an open issue. On this account, the instrumentation in the heat transfer region inside GENEVA was improved to gather the necessary temperature and void fraction profiles.
The performed experiments provide a generic and wide database concerning boiling in a LPLF natural circulation systems. Within this paper, the development of the wall and bulk fluid temperature as well as the axial and center line void fraction profile in a slightly inclined tube for different heat flow rates are discussed. Furthermore, flow patterns could be identified on behalf of the void fraction measurements. To conclude the experimental analysis, the development of the heat transfer coefficient was estimated.
These experimental data provide the basis for a simulation with the lumped-parameter thermal-hydraulic code ATHLET and serve as validation reference. However, the comparisons between the experimental and computational results show insufficient agreements. Mainly, the simulation misses the saturation point of the experiments, which leads to great differences of the void fraction values. Moreover, inaccuracies appear as well with the heat transfer coefficient.
The experimental and computational results that are discussed in this paper provide the basis for the advancement not only of heat transfer correlations but also of flow pattern maps within the range of low pressure natural circulation system. In summary, this investigation contributes to the general purpose to enhance nuclear safety by providing an accurate and reliable prediction of the heat removal capacity of passive systems.
Keywords: flow patterns; GENEVA; heat transfer coefficient; low pressure natural circulation; nuclear safety; passive systems
Experimental and Computational Multiphase Flow 1(2019)4, 286-299
- Secondary publication expected from 06.07.2020
Deterministic field-free skyrmion nucleation at a nano-engineered injector device
Finizio, S.; Zeissler, K.; Wintz, S.; Mayr, S.; Weßels, T.; Huxtable, A. J.; Burnell, G.; Marrows, C. H.; Raabe, J.
Magnetic skyrmions are topological solitons that exhibit an increased stability against annihilation [1, 2], and can be displaced with low current densities , making them a promising candidate as an information carrier . In order to demonstrate a viable skyrmion-based memory device, it is necessary to reliably and reproducibly nucleate, displace, detect, and delete the magnetic skyrmions. While the skyrmion displacement [4–7] and detection [8, 9] have both been investigated in detail, much less attention has been dedicated to the study of the sub-ns dynamics of the skyrmion nucleation and deletion processes. Only limited studies on the statics [10, 11] and above-ns dynamics  have been performed, leaving still many open questions on the dynamics of the nucleation process. Furthermore, the vast majority of the presently existing studies focus on the nucleation from random natural pinning sites [10, 12], or from patterned constrictions in the magnetic material itself [10, 11], which limit the functionality of the skyrmion-based device. Those limitations can be overcome by the fabrication of a dedicated injector device on top of the magnetic material . In this study, we investigate the nucleation of magnetic skyrmions from a dedicated nano-engineered injector, demonstrating the reliable magnetic skyrmion nucleation at the remnant state. The sub-ns dynamics of the skyrmion nucleation process were also investigated, allowing us to shine light on the physical processes driving the nucleation.
Keywords: skyrmion; nucleation; x-ray microscopy
Nano Letters 19(2019)10, 7246-7255
Zero-field dynamics stabilized by in-plane shape anisotropy in MgO-based spin-torque oscillators
Here, we demonstrate numerically that shape anisotropy in MgO-based spin-torque nano-oscillators consisting of an out-of-plane magnetized free layer and an in-plane polarizer is necessary to stabilize out-of-plane magnetization precession without the need of external magnetic fields. As the in-plane anisotropy is increased, a gradual tilting of the magnetization towards the in-plane easy direction is introduced, favouring zero-field dynamics over static in-plane states. Above a critical value, zero-field dynamics are no longer observed. The optimum ratio of in-plane shape to out-of-plane uniaxial anisotropy, for which large angle out-of-plane zero-field dynamics occur within the widest current range, is reported.
Keywords: spin-torque nano-oscillator (STNO); MgO-based magnetic tunnel junctions; tunnel magnetoresistance (TMR); spin dynamics
Tunnel magnetoresistance angular and bias dependence … (Id 27885) is supplemented by this publication
Journal of Applied Physics 125(2019)8, 083902
Spectroelectrochemical studies of the Tc(VII) reduction in aqueous electrolyte media
Rodriguez, D.; Mayordomo, N.; Brendler, V.; Müller, K.; Stumpf, T.
99Tc, a weak β-particle-emitter with a half-life of 2.13×105 years, is a strongly relevant fission product. Under repository conditions it has two main oxidation states: Tc(VII), as pertechnetate TcO4, a highly water-soluble anion not significantly sorbed on minerals or sediments, and Tc(IV), mostly found as TcO2, a solid with a low solubility product and, thus, a lower mobility .
However, in 2004 Lukens et. al.  reported the existence of non-pertechnetate species in the Hanford waste tanks and identified them as Tc(I) – carbonyl complexes. In further reports of the Pacific Northwest National Laboratory [3–7] the synthesis of Tc(I) carbonyl and nitrosyl complexes, relevant to the Hanford Site and their characterization by XAS and NMR is fully explained. More recently, Chatterjee et. al.  succeeded to stabilize Tc(VI) species to study them by spectroscopic methods (UV-vis, EPR and XPS). These works show the importance of extending the current knowledge of Tc fundamental chemistry and the need for more thermodynamic information on low-valent Tc oxidation states in order to determine the reduction mechanism from Tc(VII) to Tc(IV), which is not yet fully understood.
As a first approach, we have studied the reduction of 1 mM Tc(VII) in 1M HNO3 by applying a series of negative potentials (from -100 to -500 mV) to the solution for 30 minutes each. After this time, an aliquot was taken to measure the UV-vis spectra, as shown in figure 1. Additionally, after applying -550 mV, the solution was sealed and left at rest for 24 hours to evaluate the stability of the product formed.
Figure 1-A shows a peak around 265 nm that corresponds to Tc(VII) [9,10]. The intensity of the band decreases with decreasing the potential, which implies that Tc(VII) concentration in solution decreases due to its reduction, as expected for low potential values. The spectra of the solution after 24 hours shows that Tc(VII) is formed again, although the initial concentration is not reached.
Figure 1-B shows two signals that may correspond to the formation of other Tc oxidation states. According to Alliot et. al. , the peak around 500 nm could be assigned to the Tc(IV) formation, although it would not fully explain the increase of the signal 24 hours after the experiment. On the other hand, the three peaks formed around 370 nm after V = -350 mV most probably account for the reduction of the nitric acid, as they maintain their shape after 24 hours and, if they were non common Tc species like Tc(V) or Tc(VI), they should have disproportionated to Tc(VII) in a short time.
Even though these results are very interesting, it is necessary to combine spectroscopic and electrochemical methods and to carry out the measurements at the same time in order to obtain a clear understanding on the reduction. Moreover, in order to avoid the uncertainty due to the reaction of the electrolyte, a systematic selection of anions and cations must be done. Therefore, we have studied the reduction of Tc(VII) in 1 M of aqueous sodium nitrate (NaNO3), sodium perchlorate (NaClO4), sodium bicarbonate (NaHCO3) and sodium chloride (NaCl) by cyclic voltammetry and differential pulse voltammetry coupled with UV – vis.
This work has been developed in the frame of VESPA II project (02E11607B), supported by the German Federal Ministry for Economic Affairs and Energy (BMWi).
1 A. H. Meena and Y. Arai, Environ. Chem. Lett. 15, 241 (2017).
2 W. W. Lukens, D. K. Shuh, N. C. Schroeder and K. R. Ashley, Environ. Sci. Technol. 38, 229 (2004).
3 T. Levitskaia, A. Anderson, S. Chatterjee, H. Cho, B. M. Rapko, J. Peterson, E. D. Walter and N. M. Washton, Speciation and Oxidative Stability of Alkaline Soluble, Non-Pertechnetate Technetium, Richland, Washington, 2014.
4 T. Levitskaia, A. Andersen, S. Chatterjee, G. B. Hall, E. D. Walter and Was, Spectroscopic Properties of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste, Richland, Washington, 2015.
5 G. B. Hall, S. D. Chatterjee, T. G. Levitskaia, T. J. Martin, N. A. Wall and E. D. Walter, Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report, Richland, Washington, 2016.
6 R. J. Serne, J. V Crum, B. J. Riley and T. G. Levitskaia, Options for the Separation and Immobilization of Technetium, Richland, Washington, 2016.
7 S. Chatterjee, A. Andersen, Y. Du, M. H. Engelhard, G. B. Hall, T. G. Levitskaia, W. W. Lukens, V. Shutthanandan, E. D. Walter and N. M. Washton, Characterization of Non- Pertechnetate Species Relevant to the Hanford Tank Waste, Richland, Washington, 2017.
8 S. Chatterjee, G. B. Hall, I. E. Johnson, Y. Du, E. D. Walter, N. M. Washton and T. G. Levitskaia, Inorg. Chem. Front. 5, 2081 (2018).
9 J. Paquette and W. E. Lawrence, Can. J. Chem. 63, 2369 (1985).
10 I. Alliot, C. Alliot, P. Vitorge and M. Fattahi, Environ. Sci. Technol. 43, 9174 (2009).
Keywords: Electrochemical reduction; technetium; electrolytes; aqueous chemistry
17th international conference on the chemistry and migration behavior of actinides and fission products in the geosphere, 15.-21.09.2019, Kyoto, Japan
Terahertz-Field-Induced Time Shifts in Atomic Photoemission
Schmid, G.; Schnorr, K.; Augustin, S.; Meister, S.; Lindenblatt, H.; Trost, F.; Liu, Y.; Stojanovic, N.; Al-Shemmary, A.; Golz, T.; Treusch, R.; Gensch, M.; Kübel, M.; Foucar, L.; Rudenko, A.; Ullrich, J.; Schröter, C. D.; Pfeifer, T.; Moshammer, R.
Time delays for atomic photoemission obtained in streaking or reconstruction of attosecond bursts by interference of two-photon transitions experiments originate from a combination of the quantum mechanical Wigner time and the Coulomb-laser coupling. While the former was investigated intensively theoretically as well as experimentally, the latter attracted less interest in experiments and has mostly been subject to calculations. Here, we present a measurement of the Coulomb-laser coupling-induced time shifts in photoionization of neon at 59.4 eV using a terahertz (THz) streaking field (λ = 152 μm). Employing a reaction microscope at the THz beamline of the free-electron laser in Hamburg (FLASH), we have measured relative time shifts of up to 70 fs between the emission of 2p photoelectrons (∼38 eV) and lowenergetic (<1 eV) photoelectrons. A comparison with theoretical predictions on Coulomb-laser coupling reveals reasonably good agreement.
Physical Review Letters 122(2019), 073001
Singlet ground state in the alternating spin-1/2 chain compound NaVOAsO4
Arjun, U.; Ranjith, K. M.; Koo, B.; Sichelschmidt, J.; Skourski, Y.; Baenitz, M.; Tsirlin, A. A.; Nath, R.
We present the synthesis and a detailed investigation of structural and magnetic properties of polycrystalline NaVOAsO4 by means of x-ray diffraction, magnetization, electron spin resonance (ESR), and 75As nuclear magnetic resonance (NMR) measurements as well as density-functional band structure calculations. Temperature-dependent magnetic susceptibility, ESR intensity, and NMR line shift could be described well using an alternating spin-1/2 chain model with the exchange coupling J/kB ≃ 52 K and an alternation parameter α ≃ 0.65. From the high-field magnetization measured at T = 1.5 K, the critical field of the gap closing is found to be Hc ≃ 16 T, which corresponds to the zero-field spin gap of Δ0/kB ≃ 21.4 K. Both NMR shift and spin-lattice relaxation rate show an activated behavior at low temperatures, further confirming the singlet ground state. The spin chains do not coincide with the structural chains, whereas the couplings between the spin chains are frustrated. Because of a relatively small spin gap, NaVOAsO4 is a promising compound for further experimental studies under high magnetic fields.
Physical Review B 99(2019), 014421
Gaussian and critical scalings in the magnetoconductivity fluctuations of Y3Ba5Cu8O18 superconductor
Dias, F. T.; Vieira, V. N.; Oliveira, C. P.; Silva, D. L.; Mesquita, F.; Lima, J. R.; Wolff-Fabris, F.; Kampert, E.; Pureur, P.
We have studied the superconducting transition and the magnetoconductivity fluctuations in the polycrystalline Y3Ba5Cu8O18 (Y358) superconductor under magnetic fields upto 1 T. A two-step superconducting transition could be observed as a consequence of the granular structure of the sample, which is strongly affected by the applied magnetic field. Gaussian and genuine critical 3D-XY-E fluctuation regimes were identified. A critical scaling regime beyond 3D-XY was identified for magnetic fields upto 0.25 T, corresponding to the averaged exponent 0.19 and suggesting the occurrence of the weak first-order character of the superconducting transition. In the approximation to the zero resistance a power law regime could be observed, corresponding to the averaged exponent 2.37, which are smaller than previously reported for the Y358 system. Our results are discussed in terms of the Y358 and Yba2Cu3O7−δ (Y123) results in the literature.
International Journal of Modern Physics B 32(2018), 1850360
Magnetization beyond the Ising limit of Ho2Ti2O7
Opherden, L.; Herrmannsdörfer, T.; Uhlarz, M.; Gorbunov, D. I.; Miyata, A.; Portugall, O.; Ishii, I.; Suzuki, T.; Kaneko, H.; Suzuki, H.; Wonsitza, J.
We report that the local Ising anisotropy in pyrochlore oxides—the crucial requirement for realizing the spin-ice state—can be broken by means of high magnetic fields. For the case of the well-established classical spin-ice compound Ho2Ti2O7 the magnetization exceeds the angle-dependent saturation value of the Ising limit using ultrahigh fields up to 120 T. However, even under such extreme magnetic fields full saturation cannot be achieved. Crystal-electric-field calculations reveal that a level crossing for two of the four ion positions leads to magnetization steps at 55 and 100 T. In addition, we show that by using a field sweep rate in the range of the spin-relaxation time the dynamics of the spin system can be probed. Exclusively at 25 ns/T, a new peak of the susceptibility appears around 2 T. We argue, this signals the crossover between spin-ice and polarized correlations.
Physical Review B 99(2019), 085132
- Final Draft PDF 2,2 MB Secondary publication
Electronic band structure and proximity to magnetic ordering in the chiral cubic compound CrGe
Klotz, J.; Götze, K.; Förster, T.; Bruin, J. A. N.; Wosnitza, J.; Weber, K.; Schmidt, M.; Schnelle, W.; Geibel, C.; Rößler, U. K.; Rosner, H.
CrGe belongs to the family of cubic B20 intermetallics. From experimental investigations by susceptibility and de Haas-van Alphen (dHvA) measurements and from calculations of its electronic band structure by densityfunctional theory (DFT), CrGe is found to form a metallic paramagnetic ground state. Combining dHvA and DFT data, a detailed picture of the Fermi surface of CrGe is provided. The proximity to a magnetic longrange ordering in CrGe is suggested from a prominent thermal magnetic susceptibility. The possibility to induce magnetic long-range order in CrGe is discussed based on calculated properties for CrGe substituting Ge by As or Sn, and from a comparison with MnGe and the alloy series Cr1−xMnxGe. Owing to the noncentrosymmetric and nonsymmorphic crystal structure of CrGe, in absence of broken time reversal symmetry, its band structure is marked by forced nodal lines at the Fermi edge. Moreover, this material hosts degenerate unconventional electronic quasiparticles. In particular, CrGe exhibits a sixfold degeneracy of fermions crossing within about 5 meV of the Fermi energy at the R point of the Brillouin zone.
Physical Review B 99(2019), 085130
- Final Draft PDF 1,9 MB Secondary publication
Magnetic phase diagram and crystal-field effects in the kagome-lattice antiferromagnet U3Ru4Al12
Gorbunov, D. I.; Ishii, I.; Nomura, T.; Henriques, M. S.; Andreev, A. V.; Uhlarz, M.; Suzuki, T.; Zherlitsyn, S.; Wosnitza, J.
We report on the magnetic phase diagram of the distorted kagome-lattice antiferromagnet U3Ru4Al12 determined through measurements of magnetic and elastic properties. For field applied along the  and  axes of the hexagonal crystal structure, we find pronounced anomalies in the magnetization and elastic moduli that signal the existence of unknown magnetic phases. Our crystal-electric-field (CEF) analysis evidences interlevel quadrupolar interactions between the ground-state singlet and the first excited doublet. These interactions lead to a large softening of the shear elastic modulus C44. The large number of phases and pronounced elastic
softening suggest that geometric frustrations and CEF effects play an important role in the physical properties of U3Ru4Al12.
Physical Review B 99(2019), 054413
- Final Draft PDF 1022 kB Secondary publication
U2Ni2Sn and the origin of magnetic anisotropy in uranium compounds
Maskova, S.; Andreev, A. V.; Skourski, Y.; Yasin, S.; Gorbunov, D. I.; Zherlitsyn, S.; Nakotte, H.; Kothapalli, K.; Nasreen, F.; Cupp, C.; Cao, H. B.; Kolomiets, A.; Havela, L.
U2Ni2Sn is a member of a large family of intermetallic compounds with the tetragonal Mo2FeB2 crystal structure. It orders antiferromagnetically at 25 K with propagation vector q = (0, 0, 1/2 ). Magnetization, magnetoacoustic, and neutron-diffraction experiments on a single crystal provide evidence that the uranium moments align parallel to the c axis with the anisotropy energy of ≈170 K, indicating that U2Ni2Sn can be classified as an Ising system. The results are at variance with previous studies on polycrystals, which indicated different magnetic structure, and which were incompatible with the 5 f -5 f two-ion anisotropy model dominant in most U band systems. High-field magnetization studies exhibit a weak linear response for fields along the basal plane up to the highest field applied (60 T), while the c-axis magnetization curve exhibits three metamagnetic transitions at approximately 30, 39, and 50 T. The U magnetic moments of 0.87μB, the low magnetic entropy, and the enhanced Sommerfeld coefficient γ = 187 mJ/mol f.u.K2 suggest that U2Ni2Sn can be classified as an itinerant antiferromagnet with strong electron-electron correlations.
Physical Review B 99(2019), 064415
LISEL@DREAMS - The future of Accelerator Mass Spectrometry
LISEL (Low energy Isobar SEparation by Lasers) is a future project at the DREAMS (DREsden Accelerator Mass Spectrometry) facility to widen the applications of AMS by extending the range of measurable (radio-) nuclides. AMS has proven to be a versatile tool capable of detecting a large number of long-lived radionuclides at the ultra-trace level i.e. isotope ratios down to 1E-16. However, being a mass spectrometric method, it is limited by the presence of strong isobaric background. To overcome this limitation, we propose to remove the isobars already at the low-energy side by laser photodetachment. This method allows to selectively neutralize isobars by laser radiation, leaving the ions of interest intact. First studies were performed at the University of Vienna and gave promising results [1,2] for the easier to be measured low-mass AMS isotopes Al-26 and Cl-36. Within the LISEL project this method will be for the first time applied to an AMS facility based on a 6 MV tandem accelerator. The first isotopes to be addressed with the new method will be Mn-53 and Fe-60. Both are currently only measurable at AMS facilities with more than 10 MV terminal voltage (currently available only at the ANU in Canberra/Australia or the LMU and TU Munich in Garching/Germany). Further on we foresee to apply this method to other rare isotopes, making LISEL@DREAMS a versatile machine for all isotopes. This will subsequently widen the applications and also the user community.
 Forstner, O. et al., Nucl. Instr. And Meth. B 361 (2015) p. 217-221  Martschini, M. et al., Int. J. Mass Spectrom., 415 (2017) p. 9-17
Keywords: laser; AMS; accelerator mass spectrometry
PLATAN 2019, International Conference Merger of the Poznan Meeting on Lasers and Trapping Devices in Atomic Nuclei Research and the International Conference on Laser Probing, 19.-24.05.2019, Mainz, Deutschland
Ion Beam Physics Workshop, 24.-26.06.2019, Dresden, Deutschland
Ultrasensitive (<1 mBq), cheap, and fast detection method for ⁷Be allowing high sample throughput
Beryllium-7 (T1/2 = 53.22 d), mainly measured via γ-spectrometry, is used as a (natural) radiotracer for education and science . For activities < 0.1 Bq and especially for samples also containing so longer-lived ¹⁰Be (T1/2 = 1.387 Ma), accelerator mass spectrometry (AMS) is the method-of-choice.
We demonstrate that ⁷Be and ¹⁰Be can be quantified at the DREsden AMS (DREAMS) facility [2,3] on the same prepared BeO. Detection limits (⁷Be) are as low as ~ 0.6 mBq, hence, one-to-two orders of magnitude better than “standard/ordinary” and “sophisticated” decay counting (e.g. in an underground laboratory). Uncertainties for small samples are usually 6-7 % for small samples. The method is validated by γ-counting of two larger rainwater samples showing an excellent agreement with the AMS result .
Samples as small as tens of millilitres of rainwater can be chemically processed (after acidification) within a few hours without expensive and time-consuming ion exchange. Isobar (⁷Li) suppression by chemistry and AMS is sufficient to guarantee an ultrasensitive, cheap, and fast detection method for ⁷Be allowing high sample throughput.
The DREAMS facility allows external user access free-of-charge via a proposal system. Further information can be found at www.hzdr.de/ibc or www.ionbeamcenters.eu.
Parts of this research were carried out at the Ion Beam Centre (IBC) at the Helmholtz-Zentrum Dresden-Rossendorf e. V., a member of the Helmholtz Association. We appreciate support of Dominik Güttler, René Ziegenrücker and the DREAMS operator team during AMS-measurements, of Gyürky György (Hungarian Academy of Sciences) for providing ⁷Be for the calibration material, and of BMBF (05K16MG1) and DAAD-RISE Professional (HZDRPH-456) for funding. It was a pleasure to discuss ⁷Be-AMS with Andrew Smith (ANSTO).
 R. Querfeld, S. Merchel, G. Steinhauser, J. Radioanal. Nucl. Chem. 314 (2017) 521-527.
 S. Akhmadaliev et al., Nucl. Instr. Meth. B 294 (2013) 5-10.
 G. Rugel et al., Nucl. Instr. Meth. B 370 (2016) 94-100.
 C. Tiessen et al., Accelerator mass spectrometry (AMS) for beryllium-7 measurements in smallest rainwater samples, J. Radioanal. Nucl. Chem, 2019, doi: 10.1007/s10967-018-6371-6.
Keywords: Be-7; Be-10; accelerator mass spectrometry (AMS); rainwater
Invited lecture (Conferences)
2nd International Conference on Radioanalytical and Nuclear Chemistry (RANC 2019), 05.-10.05.2019, Budapest, Hungary
Viable and active microorganisms in the deep terrestrial biosphere
Lopez-Fernandez, M.; Simone, D.; Broman, E.; Turner, E.; Wu, X.; Bertilsson, S.; Dopson, M.
Although the continental deep biosphere is estimated to contain 2 to 19% of the earth’s total biomass, it is still one of the least understood ecosystems on the planet. A key question for the terrestrial deep biosphere is the viability and activity of the large diversity of microorganisms present. This work shows that the microbial populations in aquifers with different chemistry and depth below the surface are viable and active and their diversity decreased with depth below the surface. Quantitative PCR and high throughput 16S rRNA gene sequencing revealed no significant differences in 16S rRNA gene abundances and microbial diversity between total and viable communities. This suggested that the populations were adapted to the prevailing oligotrophic conditions and that non-viable cells are rapidly degraded and recycled into new biomass. In addition, in situ fixed RNA transcripts aligned to the three domains of life, supporting activity within these communities. Many of the SSU rRNA transcripts grouped within recently described candidate phyla or could not be mapped to known branches on the tree of life, suggesting that a large portion of the active biota in the deep biosphere remains unexplored. Despite the extremely oligotrophic conditions, mRNA transcripts revealed a diverse range of metabolic strategies carried out by different taxa. These results emphasize the need to further investigate microbial activities in the deep biosphere and the importance of unclassified and candidate phyla in this environment.
12th International Congress of Extremophiles, 16.-20.09.2018, Ischia, Italy
Depth and Dissolved Organic Carbon Shape Microbial Communities in Surface Influenced but Not Ancient Saline Terrestrial Aquifers
Lopez-Fernandez, M.; Åström, M.; Bertilsson, S.; Dopson, M.
The continental deep biosphere is suggested to contain a substantial fraction of the earth’s total biomass and microorganisms inhabiting this environment likely have a substantial impact on biogeochemical cycles. However, the deep microbial community is still largely unknown and can be influenced by parameters such as temperature, pressure, water residence times, and chemistry of the waters. In this study, 21 boreholes representing a range of deep continental groundwaters from the Äspö Hard Rock Laboratory were subjected to high-throughput 16S rRNA gene sequencing to characterize how the different water types influence the microbial communities. Geochemical parameters showed the stability of the waters and allowed their classification into three groups. These were (i) waters influenced by infiltration from the Baltic Sea with a “modern marine (MM)” signature, (ii) a “thoroughly mixed (TM)” water containing groundwaters of several origins, and (iii) deep “old saline (OS)” waters. Decreasing microbial cell numbers positively correlated with depth. In addition, there was a stronger positive correlation between increased cell numbers and dissolved organic carbon for the MM compared to the OS waters. This supported that the MM waters depend on organic carbon infiltration from the Baltic Sea while the ancient saline waters were fed by “geogases” such as carbon dioxide and hydrogen. The 16S rRNA gene relative abundance of the studied groundwaters revealed different microbial community compositions. Interestingly, the TM water showed the highest dissimilarity compared to the other two water types, potentially due to the several contrasting water types contributing to this groundwater. The main identified microbial phyla in the groundwaters were Gammaproteobacteria, unclassified sequences, Campylobacterota (formerly Epsilonproteobacteria), Patescibacteria, Deltaproteobacteria, and Alphaproteobacteria. Many of these taxa are suggested to mediate ferric iron and nitrate reduction, especially in the MM waters. This indicated that nitrate reduction may be a neglected but important process in the deep continental biosphere. In addition to the high number of unclassified sequences, almost 50% of the identified phyla were archaeal or bacterial candidate phyla. The percentage of unknown and candidate phyla increased with depth, pointing to the importance and necessity of further studies to characterize deep biosphere microbial populations.
Keywords: 16S rRNA gene; amplicon sequencing; deep subsurface; groundwaters; chemistry; microbial diversity
Frontiers in Microbiology 9(2018), 2880
Microbial Community and Metabolic Activity in Thiocyanate Degrading Low Temperature Microbial Fuel Cells
Ni, G.; Canizales, S.; Broman, E.; Simone, D.; Palwai, V. R.; Lundin, D.; Lopez-Fernandez, M.; Sleutels, T.; Dopson, M.
Thiocyanate is a toxic compound produced by the mining and metallurgy industries that needs to be remediated prior to its release into the environment. If the industry is situated at high altitudes or near the poles, economic factors require a low temperature treatment process. Microbial fuel cells are a developing technology that have the benefits of both removing such toxic compounds while recovering electrical energy. In this study, simultaneous thiocyanate degradation and electrical current generation was demonstrated and it was suggested that extracellular electron transfer to the anode occurred. Investigation of the microbial community by 16S rRNA metatranscriptome reads supported that the anode attached and planktonic anolyte consortia were dominated by a Thiobacillus-like population. Metatranscriptomic sequencing also suggested thiocyanate degradation primarily occurred via the ‘cyanate’ degradation pathway. The generated sulfide was metabolized via sulfite and ultimately to sulfate mediated by reverse dissimilatory sulfite reductase, APS reductase, and sulfate adenylyltransferase and the released electrons were potentially transferred to the anode via soluble electron shuttles. Finally, the ammonium from thiocyanate degradation was assimilated to glutamate as nitrogen source and carbon dioxide was fixed as carbon source. This study is one of the first to demonstrate a low temperature inorganic sulfur utilizing microbial fuel cell and the first to provide evidence for pathways of thiocyanate degradation coupled to electron transfer.
Keywords: MFC; thiocyanate degradation; extracellular electron transfer; low temperature; metatranscriptomics
Frontiers in Microbiology 9(2018), 2308
Metatranscriptomes Reveal That All Three Domains of Life Are Active but Are Dominated by Bacteria in the Fennoscandian Crystalline Granitic Continental Deep Biosphere
Lopez-Fernandez, M.; Simone, D.; Wu, X.; Soler, L.; Nilsson, E.; Holmfeldt, K.; Lantz, H.; Bertilsson, S.; Dopson, M.
ABSTRACT The continental subsurface is suggested to contain a significant part of the earth’s total biomass. However, due to the difficulty of sampling, the deep subsurface is still one of the least understood ecosystems. Therefore, microorganisms inhabiting this environment might profoundly influence the global nutrient and energy cycles. In this study, in situ fixed RNA transcripts from two deep continental groundwaters from the Äspö Hard Rock Laboratory (a Baltic Sea-influenced water with a residence time of < 20 years, defined as “modern marine,” and an “old saline” groundwater with a residence time of thousands of years) were subjected to metatranscriptome sequencing. Although small subunit (SSU) rRNA gene and mRNA transcripts aligned to all three domains of life, supporting activity within these community subsets, the data also suggested that the groundwaters were dominated by bacteria. Many of the SSU rRNA transcripts grouped within newly described candidate phyla or could not be mapped to known branches on the tree of life, suggesting that a large portion of the active biota in the deep biosphere remains unexplored.
Despite the extremely oligotrophic conditions, mRNA transcripts revealed a diverse range of metabolic strategies that were carried out by multiple taxa in the modern marine water that is fed by organic carbon from the surface. In contrast, the carbon dioxide- and hydrogen-fed old saline water with a residence time of thousands of years predominantly showed the potential to carry out translation. This suggested these cells were active, but waiting until an energy source episodically becomes available.
IMPORTANCE A newly designed sampling apparatus was used to fix RNA under in situ conditions in the deep continental biosphere and benchmarks a strategy for deep biosphere metatranscriptomic sequencing. This apparatus enabled the identification of active community members and the processes they carry out in this extremely oligotrophic environment. This work presents for the first time evidence of eukaryotic, archaeal, and bacterial activity in two deep subsurface crystalline rock groundwaters from the Äspö Hard Rock Laboratory with different depths and geochemical characteristics. The findings highlight differences between organic carbon fed shallow communities and carbon dioxide- and hydrogen-fed old saline waters. In addition, the data reveal a large portion of uncharacterized microorganisms, as well as the important role of candidate phyla in the deep biosphere, but also the disparity in microbial diversity when using standard microbial 16S rRNA gene amplification versus the large unknown portion of the community identified with unbiased metatranscriptomes.
Keywords: metatranscriptomes; mRNA; rRNA; deep biosphere; groundwaters
mBio 9(2018)6, e01792-18
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