A Polysiloxide Complex with two Chromium(III) η2-Superoxo Moieties

The isolation and identification of intermediates formed in the course of the activation of dioxygen at transition metal centers reveals important mechanistic insights concerning such processes. We previously reported the reaction of the dinuclear Cr^II complex [L₂Cr₂(MeCN)₂][Li(MeCN)]₂ (L=PhSi(OSiPh₂O⁻)₃) ( 5 ) with dioxygen, which resulted in the formation of the Cr^IV oxo complex [L₂Cr₂O₂][Li(THF)₂]₂ ( 6 ), as the final room temperature stable product. Here we now report the isolation and characterization of an intermediate en route to 6 , namely the dinuclear Cr^III superoxo complex [L₂Cr₂(O₂)₂][Li(MeCN)]₂ ( 7 ). 7 is the first example of a structurally characterized dinuclear Cr^III superoxo complex with two independent side-on bound superoxo ligands. Reactivity studies outline the capability of this superoxo complex to activate weak O−H bonds.     

Recycling von marinen Sekundärrohstoffen

As a waste product, oyster shells pose a major environmental pollution problem and the reuse of the material is becoming increasingly important. Since the comminution process in the recycling of secondary raw materials defines the properties of the material, oyster shells were grinded using a planetary ball mill and an impact mill and the fractions obtained were analyzed in terms of size and shape and compared with each other. A comminuted material from the impact mill was used for a series of wetting experiments, which helped to demonstrate the surface free energy of the material.     

Lignin from Annual Plants as Raw Material Source for Flavors and Basic Chemicals

The enzymatic conversion of lignins, possibly in combination with electrochemical oxidation, makes aromatics such as syringol, guaiacol, vanillin and catechol available in the qualities required by the fragrance industry. The lignins were obtained by soda digestion from wheat straw and Miscanthus, characterized and then converted with laccases. The overall yield amounted up to 9 wt % with a product spectrum confined to four substances. Catechol was the major product, with a fraction of ≈75 %. It can easily be isolated by extraction with acetone.     

Generation of high-performance code based on a domain-specific language for algorithmic skeletons

The Journal of Supercomputing - Parallel programming can be difficult and error prone, in particular if low-level optimizations are required in order to reach high performance in complex...     

Development and optimisation of a defined high cell density yeast medium

Saccharomyces cerevisiae cells grown in a small volume of chemically defined media neither reach the desired cell density nor grow at a fast enough rate to scale down the volume and increase the sample number of classical biochemical assays, as the detection limit of the readout often requires a high number of cells as an input. To ameliorate this problem, we developed and optimised a new high cell density (HCD) medium for S. cerevisiae. Starting from a widely used synthetic medium composition, we systematically varied the concentrations of all components without the addition of other compounds. We used response surface methodology to develop and optimise the five components of the medium: glucose, yeast nitrogen base, amino acids, monosodium glutamate, and inositol. We monitored growth, cell number, and cell size to ensure that the optimisation was towards a greater density of cells rather than just towards an increase in biomass (i.e., larger cells). Cells grown in the final medium, HCD, exhibit growth more similar to the complex medium yeast extract peptone dextrose (YPD) than to the synthetic defined (SD) medium. Whereas the final cell density of HCD prior to the diauxic shift is increased compared with YPD and SD about threefold and tenfold, respectively. We found normal cell-cycle behaviour throughout the growth phases by monitoring DNA content and protein expression using fluorescent reporters. We also ensured that HCD media could be used with a variety of strains and that they allow selection for all common yeast auxotrophic markers.     

Batch Tests for Optimisation of Solvent Composition and Process Flexibility of the CHALMEX FS-13 Process

ABSTRACT

Studies have been performed with the purpose of determining the optimal solvent composition of a Chalmers grouped actinide extraction (CHALMEX) solvent for the selective co-extraction of transuranic elements in a novel Grouped ActiNide EXtraction (GANEX) process. The solvent is composed of 6,6’-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]-triazin-3-yl)-[2,2’]-bipyridine (CyMe₄-BTBP) and tri-n-butyl phosphate (TBP) in phenyl trifluoromethyl sulfone (FS-13). The performance of the system has been shown to significantly depend on the ratios of the two extracting agents and the diluent to one another. Furthermore, the performance of the determined optimal solvent (10 mM CyMe₄-BTBP in 30% v/v TBP and 70% v/v FS-13) on various simulated PUREX raffinate solutions was tested. It was found that the solvent extracts all transuranic elements with high efficiency and good selectivity with regard to most other elements (fission products/activation products) present in the simulated PUREX raffinate solutions. Moreover, the solvent was found to extract a significant amount of acid. Palladium, silver, and cadmium were co-extracted along with the TRU-radionuclides, which has also been observed in other similar CHALMEX systems. The extraction of plutonium and uranium was preserved for all tested simulated PUREX raffinate solutions compared to experiments using trace amounts.     

Long-term monitoring of natural hydrogen superficial emissions in a brazilian cratonic environment. Sporadic large pulses versus daily periodic emissions

In many basins, hydrogen-emitting structures are now observed, but the estimation of the H₂ flow leading to their formation remains poorly constrained since all data show that the H₂ emissions are variable in space and time. We present here the data of a long-term monitoring campaign with a high density of permanent hydrogen detectors installed in 2 structures in the Minas Gerais State (Brazil). Results show that two kinds of signals are recorded, large sporadic pulses that affect the H₂ content of the soil for one or two days and smaller ones, with a daily periodicity, that last 6 h and during which the near surface soil concentration usually does not exceed 200 ppm. This last signal is very regular in frequency, less in amount, and the daily maximum happens around noon or in the early afternoon. We interpret the large pulses as evidences of a deep hydrogen flux, leaking either from a reservoir located in the subsurface, from an aquifer which is degassing or, although it seems unlikely, directly from the H₂ generation area.The time correlation between the pulse and the increase of the daily signal suggests that this last one corresponds to the slow release of the gas that has been captured by the soil during its transport towards the surface. This daily signal is most likely influenced by external factors such as atmospheric pressure and sub-surface bacterial activity. In map view, the lack of correlation between the highest hydrogen concentrations over time suggests that the soil is very heterogeneous and that preferential pathways exist. The results confirm that long-term monitoring, over a few months, is mandatory to catch a certain number of high pulses and so to have a better estimation of the real flow. Data also suggests that sensors with a large concentration range should be used (from 10 to several 10⁴ ppm). Even if quantification of leakage doesn't help to quantify the subsurface reserves, these new data allow a more precise evaluation of the quantity of H₂ released in surface by these structures, few hundred of kilo per day, and confirm the high H₂ prospectivity of this basin.     

Claiming participation – a comparative analysis of DIY urbanism in Denmark

The article discuss the conflicts, potentials and possible alliances of do-it-yourself (DIY) urbanism when it takes the form of spontaneous place appropriations, when it is performed as participatory urban design and when it is integrated strategically in planning. DIY urbanism and experimentation with participation are currently strong influential factors in Danish planning. The article explores the use of participatory DIY urban design in two cases: the relocation of beer drinkers in Enghave Square and the Carlsberg City development in Copenhagen, Denmark. Carlsberg City is the most thorough Danish example of how DIY urban design is employed as an investment and planning tool. It discusses the implications of DIY urbanism in terms of how it can be understood in the context of the struggles over ‘the right to the city’, how it applies different activist tactics for the appropriation of space, and how it is integrated in planning and the development logic.     

Comparison of T1-weighted 2D TSE, 3D SPGR,and two-point 3D Dixon MRI for automated segmentation of visceral adipose tissue at 3 Tesla

Objectives

To evaluate and compare conventional T1-weighted 2D turbo spin echo (TSE), T1-weighted 3D volumetric interpolated breath-hold examination (VIBE), and two-point 3D Dixon-VIBE sequences for automatic segmentation of visceral adipose tissue (VAT) volume at 3 Tesla by measuring and compensating for errors arising from intensity nonuniformity (INU) and partial volume effects (PVE).

Materials and methods

The body trunks of 28 volunteers with body mass index values ranging from 18 to 41.2 kg/m² (30.02 ± 6.63 kg/m²) were scanned at 3 Tesla using three imaging techniques. Automatic methods were applied to reduce INU and PVE and to segment VAT. The automatically segmented VAT volumes obtained from all acquisitions were then statistically and objectively evaluated against the manually segmented (reference) VAT volumes.

Results

Comparing the reference volumes with the VAT volumes automatically segmented over the uncorrected images showed that INU led to an average relative volume difference of ?59.22 ± 11.59, 2.21 ± 47.04, and ?43.05 ± 5.01 % for the TSE, VIBE, and Dixon images, respectively, while PVE led to average differences of ?34.85 ± 19.85, ?15.13 ± 11.04, and ?33.79 ± 20.38 %. After signal correction, differences of ?2.72 ± 6.60, 34.02 ± 36.99, and ?2.23 ± 7.58 % were obtained between the reference and the automatically segmented volumes. A paired-sample two-tailed t test revealed no significant difference between the reference and automatically segmented VAT volumes of the corrected TSE (p = 0.614) and Dixon (p = 0.969) images, but showed a significant VAT overestimation using the corrected VIBE images.

Conclusion

Under similar imaging conditions and spatial resolution, automatically segmented VAT volumes obtained from the corrected TSE and Dixon images agreed with each other and with the reference volumes. These results demonstrate the efficacy of the signal correction methods and the similar accuracy of TSE and Dixon imaging for automatic volumetry of VAT at 3 Tesla.