Certification of the sulphur content of three rapeseed reference materials

Summary The sulphur content of three rapeseed reference materials has been certified on the basis of measurements made by inductively coupled plasma-optical emission spectroscopy, isotope-dilution mass spectrometry and ion chromatography. Their suitability for the calibration of x-ray fluorescence spectrometers used for measuring sulphur in rapeseed samples was established.     

OPTIMAL INSTAR PARASITIZATION IN A STAGE STRUCTURED HOST-PARASITOID MODEL

A stage structured host-parasitoid model is derived and the equilibria studied. It is shown under what conditions the parasitoid controls an exponentially growing host in the sense that a coexistence equilibrium exists. Furthermore, for host populations whose inherent growth rate is not too large it is proved that in order to minimize the adult host equilibrium level it is necessary that the parasitoids attack only one of the larval stages. It is also proved in this case that the minimum adult host equilibrium level is attained when the parasitoids attack that larval stage which also maximizes the expected number of emerging adult parasitoid per larva at equilibrium. Numerical simulations tentatively indicate that the first conclusion remains in general valid for the model. However, numerical studies also show that it is not true in general that the optimal strategy will maximize the number of emerging adult parasitoid per larva at equilibrium.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Sparsely substituted chlorins as core constructs in chlorophyll analogue chemistry. II. Derivatization

Stable chlorins bearing few or no substituents have been subjected to a variety of reactions including demetalation, magnesium insertion, oxochlorin formation, and bromination followed by Suzuki coupling. The kinetics of deuteration also have been determined for two oxochlorins and a series of chlorins bearing 0, 1, 2, or 3 meso-aryl substituents.     

Systematic analysis of the PSI experiment to directly measure the sticking probabilityω s in dt fusion

Starting in 1989 an experiment was run at PSI to directly measure the final sticking probability in muon catalyzed dt fusion. This experiment was based on an active-target ionization chamber (IC) built at Gatchina, Russia, and an array of plastic neutron counters. In three runs approximately 5×10⁶ isolated alpha signals were recorded with around one half of these occurring in the inner chamber region where we have more complete understanding of the systematic errors. Particularly from a long run in 1992 we were able to obtain a very clean sticking peak of some 5000 events. However, to reach an accurate value of sticking, all systematic effects and several major backgrounds had to be understood in detail. To this end a Monte Carlo code was written to simulate the full electrostatic environment of the IC and to recreate completely each signal type including the actual tritium decay noise from the live experiment. A slightly model dependent value of approx. 0.56±0.04% is obtained for final sticking.