Use of stable isotopes as surrogates for radionuclides for security studies

During the past decade, interest has increased in qualifying and quantifying the threat posed to the public by the illegal use of radionuclides. In order to take investigations beyond the laboratory bench into more realistic scenarios, environmental and safety considerations dictate that these studies be performed on stable and benign surrogates. This paper discusses some of these studies, specifically the use of cerium dioxide for actinide ceramics and calcium and natural strontium ceramics for those based on ⁹⁰Sr.     

Analyse von Bleilegirungen

Ohne Zusammenfassung     

Ma?analytische Bestimmung des Quecksilbers

Ohne Zusammenfassung     

Nachweis und Bestimmung der Halogene

Ohne Zusammenfassung     

ChemInform Abstract: A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

Binary palladium fluorides from PdF to PdF₆ are investigated by matrix‐isolation methods using thermal evaporation and laser ablation to generate Pd atoms for reaction with F₂‐doped Ar and Ne matrices as well as neat F₂ matrices.     

Gas-phase fragmentation characteristics of benzyl-aminated lysyl-containing tryptic peptides

The fragmentation characteristics of peptides derivatized at the side-chain ε-amino group of lysyl residues via reductive amination with benzaldehyde have been examined using collision-induced dissociation (CID) tandem mass spectrometry. The resulting MS/MS spectra exhibit peaks representing product ions formed from two independent fragmentation pathways. One pathway results in backbone fragmentation and commonly observed sequence ion peaks. The other pathway corresponds to the unsymmetrical, heterolytic cleavage of the C_ζ-N_ε bond that links the benzyl derivative to the side-chain lysyl residue. This results in the elimination of the derivative as a benzylic or tropylium carbocation and a (n − l)⁺-charged peptide product (where n is the precursor ion charge state). The frequency of occurrence of the elimination pathway increases with increasing charge of the precursor ion. For the benzylmodified tryptic peptides analyzed in this study, peaks representing products from both of these pathways are observed in the MS/MS spectra of doubly-charged precursor ions, but the carbocation elimination pathway occurs almost exclusively for triply-charged precursor ions. The experimental evidence presented herein, combined with molecular orbital calculations, suggests that the elimination pathway is a charge-directed reaction contingent upon protonation of the secondary ε-amino group of the benzyl-derivatized lysyl side chain. If the secondary ε-amine is protonated, the elimination of the carbocation is observed. If the precursor is not protonated at the secondary ε-amine, backbone fragmentation persists. The application of appropriately substituted benzyl analogs may allow for selective control over the relative abundance of product ions generated from the two pathways.     

Erratum to: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

This is a correction to the following paper: Hague T, Petroczi A, Andrews PR, Barker J, Naughton DP: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Central J 2008, 2:13.     

Effects of multiple scattering, attenuation and dispersion in waveguide sensing of fish

An ocean acoustic waveguide remote sensing system can instantaneously image and continuously monitor fish populations distributed over continental shelf-scale regions. Here it is shown theoretically that the areal population density of fish groups can be estimated from their incoherently averaged broadband matched filtered scattered intensities measured using a waveguide remote sensing system with less than 10% error. A numerical Monte-Carlo model is developed to determine the statistical moments of the scattered returns from a fish group. It uses the parabolic equation to simulate acoustic field propagation in a random range-dependent ocean waveguide. The effects of (1) multiple scattering, (2) attenuation due to scattering, and (3) modal dispersion on fish population density imaging are examined. The model is applied to investigate population density imaging of shoaling Atlantic herring during the 2006 Gulf of Maine Experiment. Multiple scattering, attenuation and dispersion are found to be negligible at the imaging frequencies employed and for the herring densities observed. Coherent multiple scattering effects, such as resonance shifts, which can be significant for small highly dense fish groups on the order of the acoustic wavelength, are found to be negligible for the much larger groups typically imaged with a waveguide remote sensing system.     

Three‐dimensional imaging of chemical phase transformations at the nanoscale with full‐field transmission X‐ray microscopy

The ability to probe morphology and phase distribution in complex systems at multiple length scales unravels the interplay of nano‐ and micrometer‐scale factors at the origin of macroscopic behavior. While different electron‐ and X‐ray‐based imaging techniques can be combined with spectroscopy at high resolutions, owing to experimental time limitations the resulting fields of view are too small to be representative of a composite sample. Here a new X‐ray imaging set‐up is proposed, combining full‐field transmission X‐ray microscopy (TXM) with X‐ray absorption near‐edge structure (XANES) spectroscopy to follow two‐dimensional and three‐dimensional morphological and chemical changes in large volumes at high resolution (tens of nanometers). TXM XANES imaging offers chemical speciation at the nanoscale in thick samples (>20 µm) with minimal preparation requirements. Further, its high throughput allows the analysis of large areas (up to millimeters) in minutes to a few hours. Proof of concept is provided using battery electrodes, although its versatility will lead to impact in a number of diverse research fields.