High pressure mössbauer studies of magnetic actinide systems

Due to the wider radial extent of 5f electrons when compared to their 4f counterparts, intermetallics of the light actinides show a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant magnetism often found in transition metal compounds. One parameter which strongly influences the magnetic character of the compound is the actinide-actinide separation which can experimentally be varied by the application of high pressure. The question of 5f electron delocalization will be reviewed with respect to Moesshauer high pressure data on NpCo₂si₂, NpAl₂, NpOs₂ and new results will be presented of NpAs. The connection of hyperfine parameters with results of X-ray diffraction studies will be discussed.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany     

Control Strategy of Hardware-in-the-Loop Simulator EPOS 2.0 for Autonomous Docking Verification

This paper briefly describes the hybrid simulator system called European Proximity Operation Simulator (EPOS 2.0) and the development of the hardware-in-the-loop (HIL) docking simulation concept. A critical requirement for the docking simulation of this HIL simulator is that the 6-DOF robots in the loop have to exactly mimic the dynamic response of the two satellites during a contact operation. The main challenges to meet this requirement are in the stiffness of the robots, which is unlike that of the satellites, as well as the time delay in the HIL simulator. The paper mainly presents the impedance parameter identification concept for matching the impedance between the satellites impact model and the EPOS robots. Finally it presents the preliminary results and future work. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A systematic SAR study of C10 modified paclitaxel analogues using a combinatorial approach

A library with 63 paclitaxel analogues modified at the C10 position of paclitaxel has been prepared using parallel solution phase synthesis. Most of the C10 analogues were slightly less active than paclitaxel in the tubulin assembly assay and had reduced potency in the B16 melanoma and MCF-7 cell line cytotoxicity assays. These modifications at C10, however, did not lead to the total loss of activity, indicating that the C10 moiety of paclitaxel may not be directly involved in the drug-microtubule interactions, but could influence its binding affinity to P-glycoprotein. Approximately 50% of the analogues demonstrated better activity against the drug resistant cell line MCF7-ADR. However, the increase in activity was 10-fold at most. This result demonstrates that the cytotoxicity against this drug resistant cancer cell line is sensitive to structural changes at the C10 position of paclitaxel. It was also found that the presence of a nitrogen atom in the C10 substituent might play a role in the interaction of analogues with microtubules.     

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post‐production, in‐service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI‐MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6‐tetramethylpiperidine‐based HALS. Fragmentation mechanisms for the [M + H]⁺ ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS³ mass spectra of N‐H, N‐CH₃, N‐C(O)CH₃ and N‐OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N‐H, N‐CH₃ or N‐C(O)CH₃ functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester‐based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental calibration and field investigation of the oxygen isotopic fractionation between biogenic aragonite and water

Marine molluscs have long been recognised as potential records of palaeoclimate change using the patterns and differences in the stable isotopic composition of the carbonate shells. The aim of this study is to improve the robustness of this approach for aragonitic molluscs by completing the first experimental calibration of the fractionation between water and biogenic aragonite. Fractionation factors were calibrated by growing specimens of the freshwater mollusc Lymnaea peregra under controlled conditions of water temperature and isotopic composition. Fifteen populations of L. peregra were maintained at constant temperature and isotopic conditions for five months (at five different temperatures and using three different water compositions). Water samples and temperature measurements were taken regularly throughout the experiment. The temperature dependence of the fractionation factor, between 8 and 24 degrees C, is given by: 1000 ln alpha=16.74x(1000T(-1))-26.39 (T in Kelvin) and the relationship between temperature (T), delta(18)O(carb) and delta(18)O(wat) is given by: T=21.36-4.83xdelta(+ degrees )O(carb)-delta(+ degrees )O(wat) (T is in degrees C, delta(18)O(carb) is with respect to Vienna Pee Dee Belemnite (PDB), the International Atomic Energy Agency (IAEA) replacement standard for PDB, and delta(18)O(wat) is with respect to Vienna standard mean ocean water (VSMOW)) The outcome of the controlled experiment is compared with previous studies on synthetic, and biogenic, calcite and aragonite from field and laboratory investigations. These comparisons suggest that although a vital offset exists between the fractionation of isotopes in synthetic and biogenic aragonite for molluscs in general, there is no vital effect that is specific either to freshwater, or to individual, genera. Therefore, the calibrated relationship may be used for any freshwater or marine mollusc to derive palaeotemperatures providing the isotopic composition of the environmental water can be reliably constrained. Copyright 1999 John Wiley & Sons, Ltd.     

Effect of three-body forces on the lattice dynamics of noble metals

A simple method to generate an effective electron-ion interaction pseudopotential from the energy wave number characteristic obtained by first principles calculations has been suggested. This effective potential has been used, in third order perturbation, to study the effect of three-body forces on the lattice dynamics of noble metals. It is found that three-body forces, in these metals, do play an important role. The inclusion of such three-body forces appreciably improves the agreement between the experimental and theoretical phonon dispersion curves.     

Total synthesis of cryptophycin-24 (Arenastatin A) amenable to structural modifications in the C16 side chain

Two efficient protocols for the synthesis of tert-butyl (5S,6R,2E, 7E)-5-[(tert-butyldimethylsilyl)oxy]-6-methyl-8-phenyl-2, 7-octadienoate, a major component of the cryptophycins, are reported. The first utilized the Noyori reduction and Frater alkylation of methyl 5-benzyloxy-3-oxopentanoate to set two stereogenic centers, which became the C16 hydroxyl and C1' methyl of the cryptophycins. The second approach started from 3-p-methoxybenzyloxypropanal and a crotyl borane reagent derived from (-)-alpha-pinene to set both stereocenters in a single step and provided the dephenyl analogue, tert-butyl (5S,6R,2E)-5-[(tert-butyldimethylsilyl)oxy]-6-methyl-2, 7-octadienoate, in five steps. This compound was readily converted to the 8-phenyl compound via Heck coupling. The silanyloxy esters were efficiently deprotected and coupled to the C2-C10 amino acid fragment to provide desepoxyarenastatin A and its dephenyl analogue. The terminal olefin of the latter was further elaborated via Heck coupling. Epoxidation provided cryptophycin-24 (arenastatin A).