Conformational properties of cyanomethoxy calix[4]arenes

O-Alkylation of the dinitro calix[4]arene 2, easily available by selective ipso-nitration of the di-cyanomethyl ether 1, with allylbromide (DMF/Cs2CO3) gave tetraethers 3 and 4 with anti- and syn-orientations of the two allyl ether residues. The two possible stereoisomers of in the partial cone and 1,2-alternate conformation exist as an equilibrium mixture which could be quantitatively analysed by 1H NMR spectroscopy. The temperature dependence of this equilibrium leads to deltaH0 = -7.6 to -9.7 kJ mol(-1) in different solvents (tetrachloroethane, benzene, dimethylsulfoxide). Since 3(1,2-alt) could be obtained in pure form, its isomerisation to the equilibrium mixture with 3(paco) could be followed also kinetically. An activation energy of E(a) = 110.5 kJ mol(-1) was found for this reaction in DMSO-d6. The results were confirmed by similar studies with tetraethers 5 and 6 obtained by O-allylation of 1, although exact thermodynamic and kinetic studies were not possible in this case, since the NMR signals of the respective isomers were strongly overlapping. Single crystal X-ray structures were obtained for 2, 3(1,2-alt), 4(paco) and 5(1,2-alt).     

Stochastic modelling of tropical cyclone tracks

A stochastic model for the tracks of tropical cyclones that allows for the computerised generation of a large number of synthetic cyclone tracks is introduced. This will provide a larger dataset than previously available for the assessment of risks in areas affected by tropical cyclones. To improve homogeneity, the historical tracks are first split into six classes. The points of cyclone genesis are modelled as a spatial Poisson point process, the intensity of which is estimated using a generalised version of a kernel estimator. For these points, initial values of direction, translation speed, and wind speed are drawn from histograms of the historical values of these variables observed in the neighbourhood of the respective points, thereby generating a first 6-h segment of a track. The subsequent segments are then generated by drawing changes in theses variables from histograms of the historical data available near the cyclone’s current location. A termination probability for the track is determined after each segment as a function of wind speed and location. In the present paper, the model is applied to historical cyclone data from the western North Pacific, but it is general enough to be transferred to other ocean basins with only minor adjustments. A version for the North Atlantic is currently under preparation.     

Speciation of iron coordinated by phytosiderophores by use of HPLC with pulsed amperometric detection and AAS

Phytosiderophores of the mugineic acid family, and the respective iron species, have been separated by anion-exchange chromatography with NaOH gradient elution. Two different detection methods were used in parallel, pulsed amperometry (PAD) for phytosiderophores and atomic absorption spectrometry (AAS) for iron. This combination enables identification of separated iron species. Up to five different iron species were separated and detected within 30 min - two different phytosiderophore species, two amino acid species, and one species which has not yet been identified but which is most probably a decomposition product of phytosiderophores. The detection limit was in the low micro mol L(-1) concentration range, which is sufficiently low for determination in real plant samples, even after dilution. The method has been applied to root washings of iron-deficient wheat and barley plants and to a xylem exudate of non-deficient maize.     

Synthesis, characterization, and high-performance liquid chromatographic evaluation of C14 stationary phases containing branched and unbranched alkyl groups

Reversed-phase materials with branched and unbranched alkyl groups were prepared by modifying porous, spherical silica gel in a two-step reaction—immobilization of a trifunctional alkoxysilane (3-glycidoxypropyltrimethoxysilane) on the silica surface followed by reaction with a branched and an unbranched octanoic acid. The chromatographic sorbents were characterized by solid-state ²⁹Si and ¹³C NMR spectroscopy. The chromatographic behaviour of the stationary phases was evaluated by use of a test mixture according to the Standard Reference Material 870 set from the US National Institute of Standards and Technology, in order to study the effect of branched and unbranched alkyl chains.     

Potential pockets in the238U+238U system and their possible consequences

Within the double-folding model the separation, shape, and orientation dependence of the interaction potential is studied for two heavy ions. An effective nucleon-nucleon interaction (M3Y) derived fromG-matrix elements and based upon the Reid soft-core potential is used. Deformed Fermi-type matter densities with static quadrupole and hexadecapole deformations were utilized. The model is applied to the²³⁸U+²³⁸U system and shows dramatic dependence on the deformations and orientations.     

Energy Estimates for the Supersymmetric Nonlinear Sigma Model and Applications

We derive gradient and energy estimates for critical points of the full supersymmetric sigma model and discuss several applications.     

The Future of (Radio)-Labeled Compounds in Research and Development within the Life Science Industry

In this review the applications of isotopically labeled compounds are discussed and put into the context of their future impact in the life sciences. Especially discussing their use in the pharma and crop science industries to follow their fate in the environment, in vivo or in complex matrices to understand the potential harm of new chemical structures and to increase the safety of human society.