Electronic, Magnetic, and Magnetoresistance Properties of the n=2 Ruddlesden-Popper Phases Sr3Fe2−xCoxO7−δ (0.25≤x≤1.75)

A series of oxygen-deficient n=2 Ruddlesden-Popper phases, Sr₃Fe_2−xCo_xO_7−δ (0.25≤x≤1.75), were prepared by solid-state reactions. Temperature-dependent susceptibility and field-dependent magnetization data indicate that for x≥0.25 the dominant magnetic interactions are ferromagnetic. The onset of strong ferromagnetic interactions is evident at ∼200 K, and a transition to a cluster-glass state is observed for all compositions below ∼45 K. The temperature variation of resistivity for all the compounds shows variable-range hopping behavior with two different localization energy scales: one for T<40 K and another for T>80 K. Large negative magnetoresistance (the largest MR ∼−65% for x=0.25) is observed for all phases. The magnetic susceptibility, Mössbauer and X-ray absorption near-edge spectroscopy data indicate that the formal oxidation state of Fe is close to 4+. The key role of d delocalization in the Sr₃Fe_2−xCo_xO_7−δ system is compared to the Sr₃Fe_2−xMn_xO_7−δ series, where d localization dominates the properties.     

Design of radical-resistant amino acid residues: a combined theoretical and experimental investigation

Ab initio calculations have been used to design radical-resistant amino acid residues. Optimized structures of free and protected amino acids and their corresponding alpha-carbon-centered radicals were determined with B3-LYP/6-31G(d). Single-point RMP2/6-31G(d) calculations on these structures were then used to obtain radical stabilization energies, to examine the effect of steric repulsion between the side chains and amide carbonyl groups on the stability of alpha-carbon-centered peptide radicals. Relative to glycine, the destabilization for alanine and valine residues was found to be approximately 9 and 18 kJ mol(-1), respectively, which correlates with the reactivity of analogous amino acid residues in peptides toward hydrogen atom abstraction in conventional free radical reactions. To design amino acid residues that would resist radical reactions, strategies by which the steric effects could be magnified were considered. This resulted in the identification of tert-leucine and 3,3,3-trifluoroalanine as suitable molecules. With these amino acid residues, the destabilization of the alpha-carbon-centered radicals relative to that of glycine is increased substantially to approximately 36 and 41 kJ mol(-1), respectively. The theoretical predictions have been supported by experimental observations: a tert-leucine derivative was shown to be very slow to react with N-bromosuccinimide, while the corresponding trifluoroalanine derivative was found to be inert.     

Revisiting the form of dead time corrections for neutron coincidence counting

A standard nondestructive assay technique for determining the mass of plutonium in an item is passive neutron coincidence counting. In passive neutron coincidence counting, the dead time or rate loss corrections for the singles and doubles neutron counting rates are routinely made using empirical relationships that are based on the design and performance of the individual counter used to make the measurements. The empirical methods were developed ahead of any supporting theory for dead time losses and have worked well to date for the majority of safeguards measurement scenarios. Modern applications using highly efficient systems with short neutron lifetimes together with the challenges posed by highly multiplying items mean dead time corrections of higher fidelity are needed. While many attempts have been made to develop dead time corrections that are based on the physical principles of the measurements being performed, these corrections have often been found to be difficult to implement in a real system. For instance, Matthes and Haas developed an approach in 1985 which did not gain favor largely because the form of the doubles correction apparently required numerical integration which was difficult to implement with the computer technology of that time. A recent review into the approach that was developed by Matthes and Haas has determined that a straightforward analytical expression can be derived for the doubles correction that is similar to the singles rate correction that was developed in their original work. An analysis of the expressions is presented here to show how they relate to the traditional empirical methods. Further, we illustrate their implications and limitations. For instance the empirical methods do not address within burst losses i.e. rate related losses due to the correlated neutron bursts from fission, whereas the Matthes and Hass expression for singles counting does exhibit such an effect.     

FLUOROALKYLTHIO SUBSTITUTED AROMATIC DERIVATIVES

Abstract

Multiple fluoroalkyl substitution has been shown to occur with fluoroalkanesulfenyl chlorides on activated aromatics.     

Recent advances in the use of ionic liquids as solvents for protein-based materials and chemistry

Proteins are a diverse class of molecules that can act as catalysts and structural components. Interest in their interactions with ionic solvents is on the increase due to the tuneable possibilities for non-aqueous biocatalysis, improved thermostability of biomaterials, and possible roles in medicine, such as drug delivery and use as cell-growth scaffolds. We summarise here the recent examples of these exciting new aspects of protein-ionic solvent interactions, highlighting future directions.