The sequential analysis of long range fallout debris

A method for the determination of the principal radionuelides of Sr, Ba, Ce, Cs, Y, Zr, Nb, and W in single fallout samples containing bulk Si, Fe, and Ca is presented. The sample and added carriers are dissolved by fusion with sodium carbonate. The melt is leached first with hot water and then with hydrochloric acid. W and Cs are recovered from the water leach. Sr, Ba, Y, and the heavier rare earths appear in the hydrochloric acid leach. Ce is found in the leach residue and Nb in both the residue and the hydrochloric acid leach. The Zr and Nb in the residue are separated from Ce by absorption on an anion-exchanger from hydrochloric acid. The Zr and Nb in the hydrochloric acid leach are separated from Sr and Ba by precipitation of Sr and Ba as nitrates and then separated from Y and the heavier rare earths by absorption on the anion-exchanger. The combined Zr fractions are eluted with dilute hydrochloric acid and Nb with a hydrochloric-hydrofluoric acid mixture.     

The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O₂ with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.     

Site Preference Model for Hyperfine Impurities in Compounds

A thermodynamic model for site preferences of solute atoms in ordered binary phases is applied in this paper for substitutional and interstitial sites of the Cu₃Au, or L1₂, structure. Site preferences are found to depend on formation energies of combinations of elementary point defects and on energies for transfer of solutes among different sites. The composition dependence in compounds having a wide phase field is examined in detail. A phenomenology of site preference behavior is outlined for regular lattice sites as well as for non-lattice sites such as grain boundaries. This revised version was published online in September 2006 with corrections to the Cover Date.     

MCSCF reaction-path energetics and thermal rate-constants for the reaction of3NH with H2

Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (^3–)+H₂ (¹ _g ⁺ ) NH₂ (²B₁)+H (²S) involving the lowest triplet electronic state of NH₃ were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol^–1 agrees with the experimental value within 2 kcal mol^–1. The barrier to reaction is 23.4 kcal mol^–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H₂, whereas those of the reverse reaction are by a factor of 20 larger than those of OH₂ with H.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

Simple Sulfinate Synthesis Enables C?H Trifluoromethylcyclopropanation

A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS‐Na. The reactivity of six of these salts towards C H functionalization was field‐tested using several different classes of heterocycles.     

Models and algorithms for skip-free Markov decision processes on trees

We introduce a class of models for multidimensional control problems that we call skip-free Markov decision processes on trees. We describe and analyse an algorithm applicable to Markov decision processes of this type that are skip-free in the negative direction. Starting with the finite average cost case, we show that the algorithm combines the advantages of both value iteration and policy iteration—it is guaranteed to converge to an optimal policy and optimal value function after a finite number of iterations but the computational effort required for each iteration step is comparable with that for value iteration. We show that the algorithm can also be used to solve discounted cost models and continuous-time models, and that a suitably modified algorithm can be used to solve communicating models.     

Anomalous spreading behaviour of polyethyleneglycoldistearate monolayers at air/water interface

Spreading behaviour of the dimeric surfactant polyethylene-glycoldistearate (PEGDS) monolayer at air/water interface has been studied using surface pressure-area (π-A) isotherms as a function of temperature. The isotherms show a plateau suggesting a transition between a liquid expanded (LE) and a condensed state. The condensed state possibly arises due to nucleation and growth of multilayers from the monolayer. Isobaric measurements of bothA-T and π-T at constant area show transitions atT = 295 K. These plots suggest a melting followed by formation of condensed microcrystallites. Structure optimization carried out using various angles of orientation of the alkyl tails with respect to the backbone in PEGDS reveals tilt transitions of the tails in different states which can be related to the packing behaviour seen in the isotherms. Optical microscopy has been used to confirm the structures in these states.