Octahedral metallo-mesogens of chromium, molybdenum and tungsten with 1,4,7-trisubstituted 1,4,7-triazacyclononane and three carbonyl groups as ligands

Liquid crystalline complexes with chromium, molybdenum and with tungsten as metallic centres are reported. 1,4,7-Trisubstituted 1,4,7-triazacyclononane and three carbonyl groups are coordinated in an octahedral geometry. The observed mesophases are characterized as disordered rectangular columnar of a pyramidic type.     

Sequentially photocleavable protecting groups in solid-phase synthesis

[reaction: see text] A sequential solid-phase peptide synthesis was developed using both photolabile linker and protecting groups. The chromatic sequential lability between a tert-butyl ketone-derived linker (sensitive to irradiation at 305 nm) and a nitroveratryloxycarbonyl (NVOC) group (sensitive at 360 nm) was exploited to prepare Leu-Enkephalin in a 55% overall yield. This new strategy allows the preparation of peptides in essentially neutral medium, by avoiding the use of common deprotection reagents such as trifluoroacetic acid or piperidine.     

Distillation, on-line RP C18 preconcentration and HPLC-UV-PCO-CVAAS as a new combination for the determination of methylmercury in sediments and fish tissue

 Distillation as a way of sample digestion has been combined with on-line RP C18 preconcentration and HPLC-UV-PCO-CVAAS (high performance liquid chromatography – ultra violet – post column oxidation – cold vapour atomic absorption spectrometry) for the determination of methylmercury at background levels in sediments, soils and fish tissue. To prove the accuracy of this method, it was applied to sediment and fish tissue reference materials. The results correspond with the reference values within their error ranges. Excellent recoveries (92–95%) were obtained for the sediment samples by means of the standard addition method. The standard deviations of the sediment samples were within an acceptable range (7.2–12.5%), those of the fish samples were substantially lower (3.4–5.0%). The detection limit is 0.04 ng/g for 1 g sample weight. Received: 23 November 1995/Revised: 16 April 1996/Accepted: 20 April 1996     

Precise Quantification of Molybdate In Vitro by the FRET-Based Nanosensor ‘MolyProbe’

Molybdenum (Mo) is an essential trace element in all kingdoms of life. Mo is bioavailable as the oxyanion molybdate and gains biological activity in eukaryotes when bound to molybdopterin, forming the molybdenum cofactor. The imbalance of molybdate homeostasis results in growth deficiencies or toxic symptoms within plants, fungi and animals. Recently, fluorescence resonance energy transfer (FRET) methods have emerged, monitoring cellular and subcellular molybdate distribution dynamics using a genetically encoded molybdate-specific FRET nanosensor, named MolyProbe. Here, we show that the MolyProbe system is a fast and reliable in vitro assay for quantitative molybdate determination. We added a Strep-TagII affinity tag to the MolyProbe protein for quick and easy purification. This MolyProbe is highly stable, resistant to freezing and can be stored for several weeks at 4 °C. Furthermore, the molybdate sensitivity of the assay peaked at low nM levels. Additionally, The MolyProbe was applied in vitro for quantitative molybdate determination in cell extracts of the plant Arabidopsis thaliana, the fungus Neurospora crassa and the yeast Saccharomyces cerevisiae. Our results show the functionality of the Arabidopsis thaliana molybdate transporter MOT1.1 and indicate that FRET-based molybdate detection is an excellent tool for measuring bioavailable Mo.     

Electron energy-loss spectroscopy at incommensurately modulated crystalline and glassy Ba2TiGe2O8

Based on cluster molecular orbital calculations, high-energy resolution (ΔE?～ 0.4?eV) Ti–L_2,3 electron energy loss near-edge structures of single-crystalline and glassy Ba₂TiGe₂O₈ are interpreted. The finding that the Ti–L_2,3 near-edge structure of the Ba₂TiGe₂O₈ single crystal possesses less pronounced peaks than the glass under identical experimental conditions can be attributed to distinct distortions of the titanium environment caused by the very strong one-dimensional structural modulation hosted by the Ba₂TiGe₂O₈ crystal lattice. As lattice periodicity is absent in the glass, the titanium environment is more regular in the vitreous surroundings. Moreover, the modulation in crystalline Ba₂TiGe₂O₈ is responsible for the virtually indiscernible O–K near-edge structures of the glassy and crystalline samples.     

Minimal loading conditions for higher-order numerical homogenisation schemes

The present study deals with the formulation of minimal loading conditions for microscale applications in numerical two-scale modelling (FE²) approaches. From the homogenisation concept, a set of volume average rules constrains the microscale PDE to be solved. They are considered to be the minimal set of loading conditions and can be specified by additional polynomial or periodic assumptions, for example, on the microscale displacement field. Whereas the resulting volume integrals can be transformed into surface integrals for so-called first-order homogenisation schemes, this is not possible for a second-order homogenisation of second gradient or micromorphic effective media substituting a heterogeneous microcontinuum represented by a volume element on the microscale. Several numerical examples compare the minimal loading condition concept with standard techniques discussed in literature.